CN1271343A - Utilizing spirocyclic phenyl keto-enols as pesticides and herbicides - Google Patents

Utilizing spirocyclic phenyl keto-enols as pesticides and herbicides Download PDF

Info

Publication number
CN1271343A
CN1271343A CN98809557A CN98809557A CN1271343A CN 1271343 A CN1271343 A CN 1271343A CN 98809557 A CN98809557 A CN 98809557A CN 98809557 A CN98809557 A CN 98809557A CN 1271343 A CN1271343 A CN 1271343A
Authority
CN
China
Prior art keywords
alkyl
representative
separately
group
optional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN98809557A
Other languages
Chinese (zh)
Other versions
CN1217931C (en
Inventor
R·菲舍尔
T·布雷特施奈德
C·埃德伦
U·瓦亨多夫-纽曼
M·多林格
A·图尔贝格
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Pharma AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1271343A publication Critical patent/CN1271343A/en
Application granted granted Critical
Publication of CN1217931C publication Critical patent/CN1217931C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Indole Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

The invention relates to novel spirocyclic phenylketoenols of the formulain whichHet represents one of the groups in whichQ representsand X, Y, Z, m, n, R6, R9, R10 and R11 are each as defined in the description,to a plurality of processes and intermediates for their preparation and to their use as pesticides and herbicides.

Description

Utilizing spirocyclic phenyl keto-enols as sterilant and weedicide
The present invention relates to new utilizing spirocyclic phenyl keto-enols, its multiple preparation method and its purposes as sterilant and weedicide.
The cyclic ketones enol that more known phenyl replace is as insecticide, and miticide and/or weedicide are activated, for example 1H-aryl-pyrrolidine alkane derovatives (EP-A-456063,, EP-A-521334, EP-A-596298, EP-A-613884, EP-A-613885, DE-4440594, WO94/01997, WO95/01358, WO95/26954, WO95/20572, EP-A-0668267, WO96/25395, WO96/35664, WO97/01535 and WO97/02243).
In addition, find the Δ of some replacements 3-dihydrofuran-2-ketone derivatives has herbicidal performance (referring to DE-A-4014420).As the tetronic acid derivatives of initiator (3-(2-methyl-phenyl)-4-hydroxyl-5-(4-fluoro phenyl)-Δ for example 3-dihydrofuran-(2)-ketone) the synthetic DE-A-4014420 that also is described in.From open source literature Campbell etc., J.Chem.Soc., PerkinTrans.1, the compound of 1985 (8) the known similar structures of 1567-76, but do not mention any insect and/or acaricidal activity of killing.In addition, from EP-A528156, EP-A-0647637, WO-95/26345, WO-96/20196, WO96/25395, WO-96/35664, WO97/01535, the known 3-aryl-Δ of WO97/02243 and WO97/36868 3-dihydrofuran ketone derivatives has weeding, kills mite and insecticidal properties.
Yet, the effectiveness of these compound effects and scope, particularly the effectiveness and the scope of the effect under low applicating ratio and concentration always are not entirely satisfactory.In addition, the farm crop security of these compounds is always not enough.
Therefore, the invention provides the compound of new formula (I)
Figure A9880955700201
Wherein
X represents halogen, alkyl, alkenyl, alkynes base; alkoxyl group, alkenyl oxy, alkylthio, alkyl sulphinyl; alkyl sulphonyl, haloalkyl, halogenated alkenyl; halogenated alkoxy, halogenated alkenyl oxy, nitro; cyano group is perhaps represented its optional separately substituted phenyl, phenoxy group; thiophenyl, benzyl oxygen base or benzyl sulfenyl
Y represents hydrogen, halogen, and alkyl, alkenyl, the alkynes base, alkoxyl group, alkenyl oxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, haloalkyl, halogenated alkenyl, halogenated alkoxy, halogenated alkenyl oxy, nitro or cyano group,
Z represents halogen, alkyl, and alkenyl, the alkynes base, haloalkyl, halogenated alkenyl, alkoxyl group, alkenyl oxy, halogenated alkoxy, halogenated alkenyl oxy, nitro or cyano group,
N represents 0,1, and 2 or 3, one of group that the Het representative is following:
Figure A9880955700211
Or
Figure A9880955700212
Wherein G represents hydrogen (a) or represents one of following group:
Figure A9880955700213
E (f) or
Figure A9880955700214
Wherein
E representation metal ion Equivalent or ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1Represent alkyl, alkenyl, alkoxyalkyl, alkylthio alkyl or multi-alkoxy alkyl, it is optional separately to be replaced by halogen, and representative is optional by halogen, that alkyl or alkoxyl group replace and can insert one or more heteroatomic cycloalkyl, perhaps represent phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryl oxygen base alkyl, it can be chosen wantonly separately and be substituted
R 2Represent alkyl, alkenyl, alkoxyalkyl or multi-alkoxy alkyl, it can be chosen wantonly by halogen separately and replace, perhaps representation ring alkyl, phenyl or benzyl, it can be chosen wantonly separately and be substituted,
R 3, R 4And R 5Represent alkyl independently of one another, alkoxyl group, alkylamino, dialkyl amido, alkylthio, alkenyl thio or cycloalkyl sulfenyl, it can be chosen wantonly by halogen separately and replace, and perhaps represents phenyl, benzyl, phenoxy group or thiophenyl, it can be chosen wantonly separately and be substituted,
R 6And R 7Represent hydrogen independently of one another, represent alkyl, cycloalkyl, alkenyl, alkoxyl group or alkoxyalkyl, it can be chosen wantonly by halogen separately and replace, representative can be chosen substituted phenyl wantonly, representative can be chosen substituted benzyl wantonly, perhaps represents the ring that randomly contains aerobic or sulphur with the N atom that they connected, the Q representative
Figure A9880955700222
Or
Figure A9880955700223
R 9Represent hydrogen, represent alkyl, cycloalkyl, phenyl, benzyl or heteroaryl, it can be chosen wantonly separately and be substituted, and perhaps represents CO-R 1'; CO 2-R 2 'SO 2-R 1 'CONH 2CONHR 11Or
Figure A9880955700224
R 10Represent hydrogen or alkyl, R 11Represent alkyl or alkenyl, R 12Represent alkyl or alkenyl, m represents 0,1 or 2, R 1 'Be independent of R 1Have above for R 1The definition that provides, and R 2 'Be independent of R 2Have above for R 2The definition that provides.
Particularly according to substituent character, the compound of formula (I) can exist with the isomer mixture of geometrical isomer and/or optically active isomer or different compositions, if suitably, described mixture can split with ordinary method.The invention provides pure isomer and isomer mixture, its preparation and purposes and the composition that contains them.Just, always with reference to the compound of formula (I), still, this means pure compound below, with the mixture that also means the isomeric compound of different compositions under the suitable situation for briefly.
The definition of conjugated group Het (1)-(3) obtain following main structure (I-1)-(I-3):
Figure A9880955700231
Q wherein, G, X, Y, Z, n and m be definition as mentioned separately.
If Het represents group (1), the different definition of conjugated group G (a) then (b), (c), (d), (e), (f) and (g), obtains following main structure (I-1-a)-(I-1-g):
Figure A9880955700251
E wherein, L, M, Q, X, Y, Z, n, m, R 1, R 2, R 3, R 4, R 5, R 6And R 7As above definition separately.
If Het represents group (2), the different definition of conjugated group G (a) then (b), (c), (d), (e), (f) and (g), obtains following main structure (I-2-a)-(I-2-g):
Figure A9880955700261
E wherein, L, M, Q, X, Y, Z, n, m, R 1, R 2, R 3, R 4, R 5, R 6And R 7As above definition separately.
If Het represents group (3), the different definition of conjugated group G (a) then (b), (c), (d), (e), (f) and (g), obtains following main structure (I-3-a)-(I-3-g):
Figure A9880955700262
E wherein, L, M, Q, X, Y, Z, n, m, R 1, R 2, R 3, R 4, R 5, R 6And R 7As above definition separately.
In addition; discovery can obtain the compound of new formula (I) by one of following method: (A) when the N-acyl amino acid ester of formula (II) when carrying out intramolecular condensation in the presence of the thinner and in the presence of alkali; obtain the 3-Phenylpyrrolidine-2 of the replacement of formula (I-1-a), 4-diketone or its enol Q wherein, X, Y, Z, n and m be as above definition separately,
Figure A9880955700282
Q wherein, X, Y, Z, n and m be as above definition separately, and R 8Represent alkyl (preferred C 1-C 6-alkyl).(B) find in addition, when the carboxylicesters of formula (III) when carrying out intramolecular condensation in the presence of the thinner and in the presence of alkali, obtain the 3-phenyl-4-hydroxyl-Δ of the replacement of formula (I-2-a) 3-dihydrofuran ketone derivatives
Figure A9880955700291
Q wherein, X, Y, Z, n and m be as above definition separately,
Figure A9880955700292
Wherein Q, X, Y, Z, n, m and R 8As above definition separately.(C) find in addition, when the beta-keto carboxylicesters of formula (IV) when carrying out intramolecular cyclization in the presence of the thinner and in the presence of acid, obtain the 3-phenyl-4-hydroxyl-Δ of the replacement of formula (I-3-a) 3-dihydro-thiophene ketone derivatives
Figure A9880955700293
Q wherein, X, Y, Z, n and m be as above definition separately, Wherein Q, X, Y, Z, n, m and R 8As above definition and W represent hydrogen separately, halogen, alkyl (preferred C 1-C 6-alkyl) or alkoxyl group (preferred C 1-C 8-alkoxyl group).
In addition, find (D) if if suitably in the presence of thinner with suitably in the presence of acid binding agent, as Q wherein, X, Y, when the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-a) to (I-3-a) carries out following reaction separately, obtain wherein Q, X, Y, Z, m, n and R 1The compound α of above-mentioned as defined above separately formula (I-1-b) to (I-3-b)) with the acyl chloride reaction of formula V
Figure A9880955700302
R wherein 1As above definition and Hal represent halogen (particularly chlorine or bromine) or β) and the carboxylic acid anhydride of formula (VI) react
R 1-CO-O-CO-R 1(VI) R wherein 1As above definition; (E) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, as Q wherein, X, Y, the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-a) to (I-3-a) are during separately with the chloro-formic ester of formula (VII) or the reaction of chloroformic acid thioesters, obtain wherein Q, R 2, as above definition and L represent the compound of the above-mentioned formula (I-1-c) to (I-3-c) of oxygen separately for M, X, Y, Z, m and n
R 2-M-CO-Cl (VII) is R wherein 2With M as above definition separately; (F) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, as Q wherein, X, Y, Z, the compound of the above-mentioned as defined above separately formula of m and n (I-1-a) to (I-3-a) obtains wherein Q, R during separately with the chloro monothio manthanoate of formula (VIII) or the reaction of chloro dithio formate 2, as above definition and L represent the compound of the above-mentioned formula (I-1-c) to (I-3-c) of sulphur separately for M, X, Y, Z, m and n
Figure A9880955700311
R wherein 2With M as above definition separately; (G),, when X, Y, the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-a) to (I-3-a) react with the SULPHURYL CHLORIDE of formula (IX) separately, obtain wherein Q, R as Q wherein if if suitably in the presence of thinner and suitably in the presence of acid binding agent 3, X, Y, the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-d) to (I-3-d)
R 3-SO 2-Cl (IX) is R wherein 3As above definition; (H),, when X, Y, the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-a) to (I-3-a) react with the phosphorus compound of formula (X) separately, obtain wherein Q, L, R as Q wherein if if suitably in the presence of thinner and suitably in the presence of acid binding agent 4, R 5, X, Y, the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-e) to (I-3-e)
Figure A9880955700321
L wherein, R 4And R 5As above definition and Hal represent halogen (particularly chlorine or bromine) separately; (I) if suitably in the presence of thinner, as Q wherein, X, Y, Z, the compound of the above-mentioned as defined above separately formula of m and n (I-1-a) to (I-3-a) obtains wherein Q, E during separately with formula (XI) or metallic compound (XII) or amine reaction, X, Y, the compound Me (OR of the above-mentioned as defined above separately formula of Z, m and n (I-1-f) to (I-3-f) 13) t(XI)
Figure A9880955700322
Wherein Me represents monovalence or divalent metal (preferred as alkali or alkaline-earth metal, lithium for example, sodium, potassium, magnesium or calcium), and t represents 1 or 2, and R 13, R 14, R 15Represent hydrogen or alkyl (preferred C independently of one another 1-C 8-alkyl); (J) as Q wherein, X, Y when the compound of the above-mentioned as defined above separately formula of Z, m and n (I-1-a) to (I-3-a) carries out following reaction separately, obtains wherein Q, L, R 6, R 7, X, Y, the compound α of the above-mentioned as defined above separately formula of Z, m and n (I-1-g) to (I-3-g)) if if suitably in the presence of the thinner and suitably in the presence of catalyzer, with the isocyanic ester or the lsothiocyanates reaction of formula (XIII)
R 6-N=C=L (XIII) wherein
R 6With L as above definition separately,
Perhaps
If if β) suitably in the presence of the thinner and suitably in the presence of acid binding agent, with the urea chloride or the reaction of thiocarbamyl chlorine of formula (XIV) L wherein, R 6And R 7As above definition separately.
Therefore, formula (I-1-a), compound (I-2-a) and (I-3-a) is that preparation wherein G according to the present invention respectively represents group b), c), d), e), f) or g) one of formula (I-1), (I-2) and the important intermediate of compound (I-3).
In addition, the compound of finding new formula (I) is as sterilant, preferably has extraordinary activity as insecticide and miticide and as weedicide.
Formula (I) provides the General Definition according to compound of the present invention.Describe in detail above below and the preferred substituted of the group of listing in the structural formula hereinafter or scope:
X preferably represents halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-alkylthio, C 1-C 6-alkyl sulphinyl, C 1-C 6-alkyl sulphonyl, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro, cyano group perhaps represents it optional separately by halogen, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, phenyl, phenoxy group, thiophenyl, benzyl oxygen base or benzyl sulfenyl that nitro or cyano group replace.
Y preferably represents hydrogen, halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-alkylthio, C 1-C 6-alkyl sulphinyl, C 1-C 6-alkyl sulphonyl, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro or cyano group.
Z preferably represents halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro or cyano group.
N preferably represents 0,1,2 or 3.Het preferably represents one of following group
Figure A9880955700341
Or
Figure A9880955700342
Preferably represent one of following group of hydrogen (a) or representative: E (f)Or
Figure A9880955700344
Wherein
E representation metal ion Equivalent or ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1The preferred C that represents 1-C 20-alkyl, C 2-C 20-alkenyl, C 1-C 8-alkoxy-C 1-C 8-alkyl, C 1-C 8-alkylthio-C 1-C 8-alkyl or many-C 1-C 8-alkoxy-C 1-C 8-alkyl, it can be chosen wantonly by halogen separately and replace, and representative can be chosen wantonly by halogen, C 1-C 6-alkyl or C 1-C 6That-alkoxyl group replaces and wherein one or more (particularly maximum two) directly the methylene radical of adjacency can be randomly by oxygen and/or sulphur metathetical C 3-C 8-cycloalkyl,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl, C 1-C 6-halogenated alkoxy, C 1-C 6-alkyl sulfenyl or C 1-C 6The phenyl that-alkyl sulphonyl replaces,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl or C 1-C 6Phenyl-C that-halogenated alkoxy replaces 1-C 6-alkyl,
Representative is optional by halogen or C 1-C 65-that-alkyl replaces or 6-unit heteroaryl (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furyl or thienyl),
Representative is optional by halogen or C 1-C 6Phenoxy group-C that-alkyl replaces 1-C 6-alkyl, or
Representative is optional by halogen, amino or C 1-C 65-that-alkyl replaces or the heteroaryl oxygen base-C of 6-unit 1-C 6-alkyl (pyridyl oxygen base-C for example 1-C 6-alkyl, pyrimidyl oxygen base-C 1-C 6-alkyl or thiazolyl oxygen base-C 1-C 6-alkyl),
R 2The preferred C that represents 1-C 20-alkyl, C 2-C 20-alkenyl, C 1-C 8-alkoxy-C 2-C 8-alkyl or many-C 1-C 8-alkoxy-C 2-C 8-alkyl, it is chosen wantonly separately and is replaced by halogen,
Representative is optional by halogen, C 1-C 6-alkyl or C 1-C 6The C that-alkoxyl group replaces 3-C 8-cycloalkyl,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl or C 1-C 6Phenyl or benzyl that-halogenated alkoxy replaces.
R 3The optional C that is replaced by halogen of preferred representative 1-C 8-alkyl is perhaps represented phenyl or benzyl, and it is optional separately by halogen, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, cyano group or nitro replace.
R 4And R 5Preferably represent C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group, C 1-C 8-alkylamino, two (C 1-C 8-alkyl) amino, C 1-C 8-alkylthio, C 2-C 8-alkenyl thio, C 3-C 7-cycloalkyl sulfenyl, it is chosen wantonly separately and is replaced by halogen, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by halogen, cyano group, nitro, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl or C 1-C 4-haloalkyl replaces.
R 6And R 7Preferably represent hydrogen independently of one another, represent C 1-C 8-alkyl, C 3-C 8-cycloalkyl, C 3-C 8-alkenyl, C 1-C 8-alkoxyl group or C 1-C 8-alkoxy-C 1-C 8-alkyl, it is chosen wantonly separately and is replaced by halogen, and representative is optional by halogen, C 1-C 8-haloalkyl, C 1-C 8-alkyl or C 1-C 8The phenyl that-alkoxyl group replaces, representative is optional by halogen, C 1-C 8-haloalkyl, C 1-C 8-alkyl or C 1-C 8The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one not with the methylene radical of the direct adjacency of nitrogen-atoms by oxygen or sulphur metathetical C 3-C 6-alkylidene group.
Q preferably represents
Figure A9880955700362
Or
Figure A9880955700363
R 9The preferred hydrogen of representing, the optional C that is replaced by halogen of representative 1-C 8-alkyl, representative is optional by halogen, C 1-C 4-alkyl or C 1-C 4The C that-alkoxyl group replaces 3-C 8-cycloalkyl is perhaps represented phenyl, and benzyl or heteroaryl be pyridyl for example, pyrimidyl or thiazolyl, and it is optional separately by halogen, C 1-C 6-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group replace, and perhaps represent CO-R 1 ', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
R 10Preferred hydrogen or the C of representing 1-C 8-alkyl,
R 11And R 12Be identical or different, preferably represent C separately 1-C 6-alkyl or C 3-C 6-alkenyl.
M preferably represents 0 or 1,
R 1 'Be independent of R 1Preferably have above for R 1The definition that preferably provides,
R 2 'Be independent of R 2Preferably have above for R 2The definition that preferably provides.
X especially preferably represents fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group.
Y especially preferably represents hydrogen, fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group.
Z especially preferably represents fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-haloalkyl, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, nitro or cyano group.
N especially preferably represents 0,1 or 2.
One of group below Het especially preferably represents
Figure A9880955700371
Or
Figure A9880955700372
G especially preferably represents one of group below hydrogen (a) or the representative:
Figure A9880955700373
E (f)Or
Figure A9880955700374
Particularly (a), (b) or (c), wherein
E representation metal ion Equivalent or ammonium ion,
L represent oxygen or sulphur and
M represents oxygen or sulphur,
R 1Especially preferably represent C 1-C 16-alkyl, C 2-C 16-alkenyl, C 1-C 6-alkoxy-C 1-C 6-alkyl or C 1-C 6-alkylthio-C 1-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and perhaps representative is optional by fluorine, chlorine, C 1-C 5-alkyl or C 1-C 5The C that-alkoxyl group replaces 3-C 7-cycloalkyl,
Representative is optional by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3The phenyl that-halogenated alkoxy replaces,
Representative is optional by fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3Phenyl-C that-halogenated alkoxy replaces 1-C 4-alkyl,
Representative is optional by fluorine, chlorine, bromine or C 1-C 4The pyrazolyl that-alkyl replaces, thiazolyl, pyridyl, pyrimidyl, furyl or thienyl).
R 2Especially preferably represent C 1-C 16-alkyl, C 2-C 16-alkenyl, C 1-C 6-alkoxy-C 2-C 6-alkyl or many-C 1-C 6-alkoxy-C 2-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine,
Representative is optional by fluorine, chlorine, C 1-C 4-alkyl or C 1-C 4The C that-alkoxyl group replaces 3-C 7-cycloalkyl,
Representative is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4-alkyl, C 1-C 3-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3Phenyl or benzyl that-halogenated alkoxy replaces.
R 3The optional C that is replaced by fluorine or chlorine of preferred especially representative 1-C 6-alkyl is perhaps represented phenyl or benzyl, and it is optional separately by fluorine, chlorine, bromine, C 1-C 5-alkyl, C 1-C 5-alkoxyl group, C 1-C 3-haloalkyl, C 1-C 3-halogenated alkoxy, cyano group or nitro replace.
R 4And R 5Especially preferably represent C independently of one another 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-alkylamino, two (C 1-C 6-alkyl) amino, C 1-C 6-alkylthio, C 3-C 4-alkenyl thio or C 3-C 6-cycloalkyl sulfenyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 3-alkoxyl group, C 1-C 3-halogenated alkoxy, C 1-C 3-alkylthio, C 1-C 3-halogenated alkylthio, C 1-C 3-alkyl or C 1-C 3-haloalkyl replaces.
R 6And R 7Especially preferably represent hydrogen independently of one another, represent C 1-C 6-alkyl, C 3-C 6-cycloalkyl, C 3-C 6-alkenyl, C 1-C 6-alkoxyl group or C 1-C 6-alkoxy-C 1-C 6-alkyl, it is optional separately by halogen (particularly fluorine or chlorine) replacement, and representative is optional by halogen, C 1-C 5-haloalkyl, C 1-C 5-alkyl or C 1-C 5The phenyl that-alkoxyl group replaces, representative is optional by halogen, C 1-C 5-haloalkyl, C 1-C 5-alkyl or C 1-C 5The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one not with the methylene radical of the direct adjacency of nitrogen-atoms by oxygen or sulphur metathetical C 3-C 6-alkylidene group.
Q especially preferably represents
Figure A9880955700381
Or
R 9Especially preferably represent hydrogen, the optional C that is replaced by fluorine or chlorine of representative 1-C 6-alkyl is represented C 3-C 7-cycloalkyl perhaps represents it optional separately by fluorine, chlorine, bromine, C 1-C 5-alkyl, C 1-C 4-alkoxyl group, C 1-C 2-haloalkyl, C 1-C 2-halogenated alkoxy, phenyl or benzyl that nitro or cyano group replace, pyrimidyl or thiazolyl are perhaps represented CO-R 1 ', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
Figure A9880955700391
R 10Especially preferably represent hydrogen or C 1-C 6-alkyl,
R 11And R 12Be identical or different, especially preferably represent C separately 1-C 4-alkyl.
M especially preferably represents 1,
R 1 'Be independent of R 1Especially preferably have above for R 1The definition that especially preferably provides,
R 2 'Be independent of R 2Especially preferably have above for R 2The definition that especially preferably provides.
X very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, difluoro-methoxy, trifluoromethoxy, nitro or cyano group.
Y very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, difluoro-methoxy, trifluoromethoxy, nitro or cyano group.
Z very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, difluoro-methoxy, trifluoromethoxy, nitro or cyano group.
N very particularly preferably represents 0,1 or 2, and particularly 0 or 1.
Het very particularly preferably represents one of following group
Figure A9880955700401
Or
Figure A9880955700402
G very particularly preferably represents one of group below hydrogen (a) or the representative:
Figure A9880955700403
E (f)Or Particularly (b) or (c),
Wherein
E representation metal ion Equivalent or ammonium ion,
L represent oxygen or sulphur and
M represents oxygen or sulphur,
R 1Very particularly preferably represent C 1-C 14-alkyl, C 2-C 14-alkenyl, C 1-C 4-alkoxy-C 1-C 6-alkyl or C 1-C 4-alkylthio-C 1-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and perhaps representative is optional by methyl, ethyl, the C that the tertiary butyl or methoxyl group replace 3-C 6-cycloalkyl,
Representative is optional by fluorine, chlorine, and bromine, cyano group, nitro, methyl, methoxyl group, the phenyl that trifluoromethyl or trifluoromethoxy replace,
Representative is optional by fluorine, chlorine, and bromine, methyl, methoxyl group, the benzyl that trifluoromethyl or trifluoromethoxy replace,
Representative is optional separately by fluorine, chlorine, bromine or methyl substituted furyl, thienyl or pyridyl.
R 2Very particularly preferably represent C 1-C 14-alkyl, C 2-C 14-alkenyl or C 1-C 4-alkoxy-C 2-C 6-alkyl,
The optional C that is replaced by methyl or methoxy of representative 3-C 6-cycloalkyl,
Representative is optional separately by fluorine, chlorine, bromine, cyano group, nitro, methyl, methoxyl group, phenyl or benzyl that trifluoromethyl or trifluoromethoxy replace.
R 3Very particularly preferably the methyl that is replaced by fluorine or chlorine, ethyl, n-propyl, sec.-propyl are chosen in representative separately wantonly, perhaps represent phenyl or benzyl, it is optional separately by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy, trifluoromethyl, trifluoromethoxy, cyano group or nitro replace.
R 4And R 5Very particularly preferably represent C independently of one another 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino or C 1-C 4-alkylthio, it is chosen wantonly separately and is replaced by fluorine or chlorine, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 2-alkoxyl group, C 1-C 2-fluoroalkyl, C 1-C 2-alkylthio, C 1-C 2-fluoroalkane sulfenyl or C 1-C 3-alkyl replaces.
R 6And R 7Very particularly preferably represent hydrogen independently of one another, represent C 1-C 4-alkyl, C 3-C 6-cycloalkyl, C 3-C 4-alkenyl, C 1-C 4-alkoxyl group or C 1-C 4-alkoxy-C 1-C 4-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and representative is optional by fluorine, chlorine, bromine, trifluoromethyl, the phenyl that methyl or methoxy replaces, representative is chosen wantonly by fluorine, chlorine, bromine, C 1-C 4-haloalkyl, C 1-C 4-alkyl or C 1-C 4The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one can be by oxygen or sulphur metathetical C with the methylene radical of the direct adjacency of nitrogen-atoms 5-C 6-alkylidene group.
Q very particularly preferably represents
Figure A9880955700411
Figure A9880955700412
Or
Figure A9880955700413
R 9Very particularly preferably represent hydrogen, represent C 1-C 4-alkyl is represented C 3-C 6-cycloalkyl is perhaps represented phenyl or benzyl, and it is optional separately by fluorine, chlorine, and bromine, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxyl group, trifluoromethyl, trifluoromethoxy, nitro or cyano group replace, and perhaps represent CO-R 1 ', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
Figure A9880955700421
R 10Very particularly preferably represent hydrogen or methyl,
R 11And R 12Be identical or different, very particularly preferably represent methylidene or ethyl separately.
M very particularly preferably represents 1,
R 1 'Be independent of R 1Very particularly preferably have above for R 1The definition that very particularly preferably provides,
R 2 'Be independent of R 2Very particularly preferably have above for R 2The definition that very particularly preferably provides.
Above-mentioned general or preferred group definition or explanation can be made up as required mutually, promptly comprise the combination between described scope and the preferable range.They are applicable to that promptly end product also correspondingly is applicable to precursor and intermediate.
Compound for the formula (I) that wherein contains the combination that above-mentioned conduct preferred (preferably) defines provides preferred version of the present invention.
Compound for the formula (I) of the combination that wherein contains the special preferred definition of above-mentioned conduct provides the special preferred version of the present invention.
Compound for the formula (I) that wherein contains the combination that above-mentioned conduct very particularly preferably defines provides very particularly preferably scheme of the present invention.
Saturated or unsaturated alkyl, for example alkyl or alkenyl, and with heteroatomic combination in, for example the alkyl in alkoxyl group in all cases, whenever possible, can be a straight or branched.
Optional substituted alkyl can be one or polysubstituted, and substituting group can be identical or different under polysubstituted various situations.
The compound of in preparation embodiment, mentioning, can specifically mention the compound of following formula (I-1-a):
Figure A9880955700431
Table 1:m=1
Figure A9880955700441
?X ?Y ?Z n ??X ?Y ??Z n
?CH 3 ?H ?H ?CH 3 ?Br ??6-Cl
?CH 3 ?CH 3 ?H ?CH 3 ?Cl ??6-Br
?CH 3 ?H ?5-CH 3 ?Br ?CH 3 ??6-Cl
?CH 3 ?H ?6-CH 3 ?CH 3 ?CH 3 ??6-CN
?CH 3 ?CH 3 ?5-CH 3 ?CH 3 ?CN ??6-CH 3
?CH 3 ?CH 3 ?6-CH 3 ?CH 3 ?CH 3 ??6-OCH 3
?CH 3 ?CH 3 ?3，5-(CH 3) 2 ?CH 3 ?OCH 3 ??6-CH 3
?CH 3 ?CH 3 ?3，6-(CH 3) 2 ?Cl ?Cl ??5-Cl
?CH 3 ?Cl ??H ?CH 3 ?Cl ??5-CH 3
?Cl ?CH 3 ??H ?Br ?CH 3 ??5-Cl
?Cl ?H ??6-F ?Br ?CH 3 ??5-CH 3
?CH 3 ?H ??6-Cl ?CH 3 ?Br ??5-Cl
?Cl ?H ??6-Cl ?Cl ?Cl ??5-CH 3
?CH 3 ?Cl ??6-Cl ?CH 3 ?Br ??5-CH 3
?CH 3 ?Br ??5-Br ?Cl ?CH 3 ??5-Cl
?Cl ?CH 3 ??6-Cl ?CH 3 ?CH 3 ??5-Br
?Br ?CH 3 ??6-Br ?CH 3 ?H ??3-Cl，6-CH 3
?CH 3 ?Cl ??6-CH 3 ?CH 3 ?H ??3-Br，6-CH 3
?CH 3 ?CH 3 ??6-Cl ?Cl ?CF 3 ??6-Cl
?CH 3 ?Br ??6-CH 3
?CH 3 ?CH 3 ??6-Br
Compound table 2:X, Y and the Z of table 2-8 formula (I-1-a) nAs described in Table 1
m＝1
Q=＞C=O shows 3:X, Y and Z nAs described in Table 1
m＝1
Q=＞C=N-OCH 3Table 4:X, Y and Z nAs described in Table 1
m＝1
Q=＞C=N-OC 2H 5Table 5:X, Y and Z nAs described in Table 1
m＝1
Q=＞C=N-NHCOCH 3Table 6:X, Y and Z nAs described in Table 1
m＝1
Q=＞C=N-NHCO 2C 2H 5Table 7:X, Y and Z nAs described in Table 1
m＝1
Q=＞C=N-NHSO 2CH 3Table 8:X, Y and Z nAs described in Table 1
m＝1
Figure A9880955700451
The compound of in preparation embodiment, mentioning, can specifically mention the compound of following formula (I-2-a):
Figure A9880955700461
Table 9:m=1
Figure A9880955700471
??X ?Y ?Z n ?X ?Y ?Z n
?CH 3 ?H ?H ?CH 3 ?Br ?6-Cl
?CH 3 ?CH 3 ?H ?CH 3 ?Cl ?6-Br
?CH 3 ?H ?5-CH 3 ?Br ?CH 3 ?6-Cl
?CH 3 ?H ?6-CH 3 ?CH 3 ?CH 3 ?6-CN
?CH 3 ?CH 3 ?5-CH 3 ?CH 3 ?CN ?6-CH 3
?CH 3 ?CH 3 ?6-CH 3 ?CH 3 ?CH 3 ?6-OCH 3
?CH 3 ?CH 3 ?3，5-(CH 3) 2 ?CH 3 ?OCH 3 ?6-CH 3
?CH 3 ?CH 3 ?3，6-(CH 3) 2 ?Cl ?Cl ?5-Cl
?CH 3 ?Cl ?H ?CH 3 ?Cl ?5-CH 3
?Cl ?CH 3 ?H ?Br ?CH 3 ?5-Cl
?Cl ?H ?6-F ?Br ?CH 3 ?5-CH 3
?CH 3 ?H ?6-Cl ?CH 3 ?Br ?5-Cl
?Cl ?H ?6-Cl ?Cl ?Cl ?5-CH 3
?CH 3 ?Cl ?6-Cl ?CH 3 ?Br ?5-CH 3
?CH 3 ?Br ?5-Br ?Cl ?CH 3 ?5-Cl
?Cl ?CH 3 ?6-Cl ?CH 3 ?CH 3 ?5-Br
?Br ?CH 3 ?6-Br ?CH 3 ?H ?3-Cl，6-CH 3
?CH 3 ?Cl ?6-CH 3 ?CH 3 ?H ?3-Br，6-CH 3
?CH 3 ?CH 3 ?6-Cl ?Cl ?CF 3 ?6-Cl
?CH 3 ?Br ?6-CH 3
?CH 3 ?CH 3 ?6-Br
Compound table 10:X, Y and the Z of table 10-16 formula (I-2-a) nAs described in Table 9
m＝1
Q=＞C=O shows 11:X, Y and Z nAs described in Table 9
m＝1
Q=＞C=N-OCH 3Table 12:X, Y and Z nAs described in Table 9
m＝1
Q=＞C=N-OC 2H 5Table 13:X, Y and Z nAs described in Table 9
m＝1
Q=＞C=N-NHCOCH 3Table 14:X, Y and Z nAs described in Table 9
m＝1
Q=＞C=N-NHCO 2C 2H 5Table 15:X, Y and Z nAs described in Table 9
m＝1
Q=＞C=N-NHSO 2CH 3Table 16:X, Y and Z nAs described in Table 9
m＝1
Figure A9880955700481
The compound of in preparation embodiment, mentioning, can specifically mention the compound of following formula (I-3-a): Table 17:m=1
?X ?Y ?Z n ?X ?Y ??Z n
?CH 3 ?H ?H ?CH 3 ?Br ?6-Cl
?CH 3 ?CH 3 ?H ?CH 3 ?Cl ?6-Br
?CH 3 ?H ?5-CH 3 ?Br ?CH 3 ?6-Cl
?CH 3 ?H ?6-CH 3 ?CH 3 ?CH 3 ?6-CN
?CH 3 ?CH 3 ?5-CH 3 ?CH 3 ?CN ?6-CH 3
?CH 3 ?CH 3 ?6-CH 3 ?CH 3 ?CH 3 ?6-OCH 3
?CH 3 ?CH 3 ?3，5-(CH 3) 2 ?CH 3 ?OCH 3 ?6-CH 3
?CH 3 ?CH 3 ?3，6-(CH 3) 2 ?Cl ?Cl ?5-Cl
?CH 3 ?Cl ?H ?CH 3 ?Cl ?5-CH 3
?Cl ?CH 3 ?H ?Br ?CH 3 ?5-Cl
?Cl ?H ?6-F ?Br ?CH 3 ?5-CH 3
?CH 3 ?H ?6-Cl ?CH 3 ?Br ?5-Cl
?Cl ?H ?6-Cl ?Cl ?Cl ?5-CH 3
?CH 3 ?Cl ?6-Cl ?CH 3 ?Br ?5-CH 3
?CH 3 ?Br ?5-Br ?Cl ?CH 3 ?5-Cl
?Cl ?CH 3 ?6-Cl ?CH 3 ?CH 3 ?5-Br
?Br ?CH 3 ?6-Br ?CH 3 ?H ?3-Cl，6-CH 3
?CH 3 ?Cl ?6-CH 3 ?CH 3 ?H ?3-Br，6-CH 3
?CH 3 ?CH 3 ?6-Cl ?Cl ?CF 3 ?6-Cl
?CH 3 ?Br ?6-CH 3
?CH 3 ?CH 3 ?6-Br
Compound table 18:X, Y and the Z of table 18-24 formula (I-3-a) nAs described in Table 17
m＝1
Q=＞C=O shows 19:X, Y and Z nAs described in Table 17
m＝1
Q=＞C=N-OCH 3Table 20:X, Y and Z nAs described in Table 17
m＝1
Q=＞C=N-OC 2H 5Table 21:X, Y and Z nAs described in Table 17
m＝1
Q=＞C=N-NHCOCH 3Table 22:X, Y and Z nAs described in Table 17
m＝1
Q=＞C=N-NHCO 2C 2H 5Table 23:X, Y and Z nAs described in Table 17
m＝1
Q=＞C=N-NHSO 2CH 3Table 24:X, Y and Z nAs described in Table 17
m＝1
Figure A9880955700511
Use N-[(2,4,6-trimethylammonium-phenyl)-ethanoyl]-1-amino-4-methoxyimino hexanaphthene-carboxylate methyl ester is the initiator according to method (A), then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700521
Use O-[(2,4-two chloro-phenyl according to method (B))-ethanoyl]-1-hydroxyl-4-oxo-hexanaphthene-carboxylic acid, ethyl ester, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700522
Use 2-[2,4-dimethyl-phenyl according to method (C)]-4-(4-methoxyl group)-benzyl sulfenyl-4,4-(3-oxo-pentamethylene)-ethyl 3-oxobutanoate, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700523
Use 3-[(2-chloro-4-methyl according to method (D α))-phenyl]-5, the 5-[(3-phenylimino)-pentamethylene]-tetramethyleneimine-2,4-diketone and pivalyl chloride are initiator, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700531
Use 3-[(4-chloro-2-methyl according to method (D β))-phenyl]-4-hydroxyl-5,5-[(3-benzyl imino-)-pentamethylene]-Δ 3-dihydrofuran-2-ketone and diacetyl oxide are initiator, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700532
Use 3-[(2,4-two chloro-6-methyl according to method (E))-phenyl]-5,5-[(3-oxo-pentamethylene]-tetramethyleneimine-2,4-diketone and chloroformic acid ethoxy ethyl ester are initiator, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700533
Changing method α according to method (F) uses 3-[(2-chlorine)-phenyl]-4-hydroxyl-5,5-[3-(2-ethanoyl diazanyl)-pentamethylene]-Δ 3-dihydrofuran-2-ketone and chloro monothio methyl-formiate are initiator, then can represent by following reaction formula according to the process of the inventive method:
Figure A9880955700541
Use 3-[(2,6-two chloro-4-methyl according to method (G))-phenyl]-4-hydroxyl-4, the 4-[(3-methoxyimino)-pentamethylene]-Δ 3-dihydrofuran-2-ketone and methylsulfonyl chloride are initiator, and then the process of this reaction can be represented by following reaction formula:
Figure A9880955700542
Use 3-[(2,5-two chloro-phenyl according to method (H)]-5,5-[(3-oxa--pentamethylene]-tetramethyleneimine-2,4-diketone and methylthio group sulfonic acid 2,2,2-trifluoroethyl ester acyl chlorides is an initiator, then the process of this reaction can be represented by following reaction formula:
Figure A9880955700543
Use 3-[(2,4-two chloro-phenyl according to method (I)]-5, the 5-[(3-ethoxy imino)-pentamethylene]-tetramethyleneimine-2,4-diketone and NaOH are initiator, then the process of this reaction can be represented by following reaction formula:
Use 3-[(2,4,5-trimethylammonium according to method (J α))-phenyl]-4-hydroxyl-5, the 5-[(2-oxo)-tetramethylene]-Δ 3-dihydrofuran-2-ketone and ethyl isocyanate are initiator, and then the process of this reaction can be represented by following reaction formula:
Use 3-[2,3,4,6-tetramethylphenyl according to method (J β)]-5, the 5-[(4-methoxyimino)-pentamethylene]-tetramethyleneimine-2,4-diketone and dimethylcarbamyl chloride are initiator, then the process of this reaction can be represented by following reaction formula:
Figure A9880955700553
Need be new with the compound that acts on according to the formula (II) of the initiator of the inventive method (A), Wherein Q, X, Y, Z, m, n and R 8As above definition separately.
For example, (Chem.Review 52,237-416 (1953) when with the amino acid derivative of phenyl acetyl halide acidylate formula (XV) of the replacement of formula (XVI); Bhattacharya, IndianJ.Chem.6,341-5,1968), perhaps when the acylamino acid of formula (XVII) is esterified (Chem.Ind. (London) 1568 (1968)) obtains the acyl amino acid ester of formula (II) Q wherein 1, m and R 8As above definition separately,
Figure A9880955700563
X wherein, Y, Z and n separately as above definition and Hal represent chlorine or bromine,
Figure A9880955700571
Q wherein, m, X, Y, Z and n be as above definition separately.
(XVII) compound is new, Q wherein, m, X, Y, Z and n be as above definition separately.
For example, when during with the amino acid of phenyl carboxylic acid halides acidylate formula (XVIII) of the replacement of formula (XVI), obtaining the compound of formula (XVII) according to Schotten-Baumann
Figure A9880955700573
Wherein Q and m as above definition separately, As above definition and Hal represent chlorine or bromine (Berlin 1977, p.505) for Organikum, VEB Deutscher Verlag derWissenschaften separately for X wherein, Y, Z and n.
In the compound of formula (XVI) some are known.It can prepare by ordinary method (referring to, Henecka for example, Houben-Weyl, Methoden der OrganischenChemie, Vol.8, p.467-469 (1952)), perhaps their patent applications of quoting from this paper beginning or known from WO98/05638 and WO97/36868.
In addition, the phenyl acetyl halide reaction of the amino-nitrile that can be by making formula (XIX) and the replacement of formula (XVI) obtains the compound of formula (XX), and these compounds then carry out acid alcohol to be separated, and prepares the initiator of the formula (II) of use in aforesaid method (A)
Figure A9880955700582
Wherein Q, X, Y, Z, m, n and R 8As above definition separately, Wherein Q and m as above definition separately,
Figure A9880955700592
X wherein, Y, Z, n and Hal be as above definition separately,
Figure A9880955700593
Q wherein, X, Y, Z, m and n be as above definition separately.
The compound of formula (XX) also is new.
For example, the route of synthesis of the intermediate of following reaction formula formula (II).
Capitalization after some structural formula numberings is used for distinguishing the different meanings of Q.Some also are used to prepare embodiment.
In the reaction formula below, with reference to the compound of following structural formula Wherein Q and m as above define.
In reaction formula, provided compound for different meanings and the m=1 of Q in the mode of embodiment.In any case, these meanings are that the structural formula that provides above is included.
In radicals R 11Can also represent optional together by methyl-or the C of ethyl-replacement 2-C 3-alkane 2 basis group.
Reaction formula 1:
Figure A9880955700611
Reaction formula 1a: Reaction formula 2:
Need be new with the compound that acts on according to the formula (III) of the initiator of the inventive method (B),
Figure A9880955700641
Q wherein 1, X, Y, Z, m, n and R 8As above definition separately.
These compounds can prepare in simple mode by known method in principle.
Like this, for example, when with the 2-hydroxycarboxylic acid esters of phenyl acetyl halide acidylate formula (XXI) of the replacement of formula (XVI), obtain the compound of formula (III)
Figure A9880955700642
Wherein Q, m and R 8As above definition separately, X wherein, Y, Z, n and Hal be as above definition (Chem.Reviews 52,237-416 (1953)) separately.
For example, the route of synthesis of the end product of the intermediate of following reaction formula formula (III) and formula (I).
Capitalization after some structural formula numberings is used for distinguishing the different meanings of Q.Some also are used to prepare embodiment.
In the reaction formula below, with reference to the compound of following structural formula
Figure A9880955700651
Wherein Q and m as above definition separately.
In reaction formula, provided compound for different meanings and the m=1 of Q in the mode of embodiment.In any case, these meanings are that the structural formula that provides above is included.
In radicals R 11Can also represent optional together by methyl-or the C of ethyl-replacement 2-C 3-alkane 2 basis group.
Reaction formula 3:
Figure A9880955700661
Reaction formula 3a: Need be new with the compound of the formula (IV) of the initiator that acts on top method (C),
Figure A9880955700681
Wherein Q, W, X, Y, Z, m, n and R 8As above definition separately.
These compounds can be by known method preparation in principle.
For example, when with the phenylacetic acid ester of 2-benzyl sulfenyl-carboxylic acid halides replacement of acidylate formula (XXII) in the presence of highly basic of formula (XXIII), obtain the compound of formula (IV)
Figure A9880955700682
Wherein X, Y, Z, n and R 8As above definition separately,
Figure A9880955700683
Wherein Q and W separately as above definition and Hal represent halogen (particularly chlorine or bromine) (referring to, M.S.Chambers for example, E.J.Thomas, D.J.Williams, J.Chem.Soc.Chem.Commun., (1987), 1228).
Compound from more known formulas of above-cited patent application (XXII).For example, when the compound of esterification formula (XXIV) in the presence of pure and mild dewatering agent (for example vitriol oil), perhaps when with the compound acylation alcohol of formula (XVI), obtain the compound of formula (XXII)
Figure A9880955700691
X wherein, Y, Z and n be as above definition separately, X wherein, Y, Z, n and Hal be as above definition (Chem.Reviews 52,237-416 (1953)) separately.
Benzyl sulfenyl-the carboxylic acid halides of formula (XXIII) is new.It can prepare by currently known methods (the microbiotic magazine (J.Antibiotics (1983), 26,1589, WO95/26345).
Also need to carry out according to the inventive method D with acting on; E; F; G; H; the acyl halide of the formula V of the initiator of I and J; the carboxylic acid anhydride of formula (VI); the chloro-formic ester of formula (VII) or chloroformic acid thioesters; the chloro monothio manthanoate of formula (VIII) or chloro dithio formate, the SULPHURYL CHLORIDE of formula (IX), the phosphorus compound of formula (X) and formula (XI) and metal hydroxides (XII); metal alkoxide or amine, the urea chloride of the isocyanic ester of formula (XIII) and formula (XIV) generally is known organic or inorganic chemical compound.
In addition, the compound from the known formula V of above-mentioned patent application to (XIV), perhaps they can prepare by the method that the application describes.
Method (A) is characterised in that, makes wherein Q, X, Y, Z, m, n and R 8The compound of formula (II) carries out intramolecular condensation in the presence of alkali as defined above separately.
In the basis method of (A), the Q in the formula (II) also can represent group X wherein, Y, Z and n be as above definition separately.This also is applicable to the definition according to the Q in the method Chinese style (III) of (B).
The suitable diluent that is used for according to the inventive method (A) is all inert organic solvents.The preferred hydro carbons that uses, for example toluene and dimethylbenzene also have ethers, dibutyl ether for example, tetrahydrofuran (THF) ， diox, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether also have polar solvent, for example methyl-sulphoxide, tetramethylene sulfone, dimethyl formamide and N-methyl-pyrrolidone, and alcohols, methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol.
When carrying out the method according to this invention (A), all conventional proton acceptors can be used as alkali (proton-removed agent).Preferred basic metal and the alkaline earth metal oxide of using, oxyhydroxide and carbonate, sodium hydroxide for example, potassium hydroxide, magnesium oxide, calcium oxide, yellow soda ash, salt of wormwood and lime carbonate, it also can be at phase-transfer catalyst triethyl benzyl ammonia chloride for example, Tetrabutyl amonium bromide, Adogen 464 (=methyl trialkyl (C 8-C 10) ammonium chloride) or TDA1 (=three-(methoxyethoxyethyl)-amine) existence use down.In addition, can use basic metal, for example sodium or potassium.Can also use basic metal and alkaline-earth metal amide and hydride, ammonification sodium for example, sodium hydride and hydrolith also have alkali metal alcoholates, for example sodium methylate, sodium ethylate and potassium tert.-butoxide.
When carrying out the inventive method (A), temperature of reaction can change in sizable scope.Generally speaking, be reflected under the temperature between 0 ℃ and 250 ℃, preferably under the temperature between 50 ℃ and 150 ℃, carry out.
The inventive method (A) is generally under atmospheric pressure carried out.
When carrying out the inventive method (A), the reacted constituent of formula (II) and deprotonation alkali generally use with mole such as about to twice molar weight.But also can use big relatively excessive (maximum 3 moles) one or another kind of composition.
Method (B) is characterised in that, makes wherein Q, X, Y, Z, m, n and R 8The compound of formula (III) is carrying out intramolecular condensation in the presence of the thinner and in the presence of alkali as defined above separately.
The suitable diluent that is used for according to the inventive method (B) is all inert organic solvents.The preferred hydro carbons that uses, for example toluene and dimethylbenzene also have ethers, dibutyl ether for example, tetrahydrofuran (THF) ， diox, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether also have polar solvent, for example methyl-sulphoxide, tetramethylene sulfone, dimethyl formamide and N-methyl-pyrrolidone, and alcohols, methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol.
When carrying out the method according to this invention (B), all conventional proton acceptors can be used as alkali (proton-removed agent).Preferred basic metal and the alkaline earth metal oxide of using, oxyhydroxide and carbonate, sodium hydroxide for example, potassium hydroxide, magnesium oxide, calcium oxide, yellow soda ash, salt of wormwood and lime carbonate, it also can be at phase-transfer catalyst triethyl benzyl ammonia chloride for example, Tetrabutyl amonium bromide, Adogen 464 (=methyl trialkyl (C 8-C 10) ammonium chloride) or TDA1 (=three-(methoxyethoxyethyl)-amine) existence use down.In addition, can use basic metal, for example sodium or potassium.Can also use basic metal and alkaline-earth metal amide and hydride, ammonification sodium for example, sodium hydride and hydrolith also have alkali metal alcoholates, for example sodium methylate, sodium ethylate and potassium tert.-butoxide.
When carrying out the inventive method (B), temperature of reaction can change in sizable scope.Generally speaking, be reflected under the temperature between 0 ℃ and 250 ℃, preferably under the temperature between 50 ℃ and 150 ℃, carry out.
The inventive method (B) is generally under atmospheric pressure carried out.
When carrying out the inventive method (B), the reacted constituent of formula (III) and deprotonation alkali generally use with mole such as about.But also can use big relatively excessive (maximum 3 moles) one or another kind of composition.
Method (C) is characterised in that, makes wherein Q, W, X, Y, Z, m, n and R 8Separately as defined above formula (IV) if compound in the presence of acid and suitably in the presence of thinner, carry out intramolecular cyclization.
The suitable diluent that is used for according to the inventive method (C) is all inert organic solvents.The preferred hydro carbons that uses, for example toluene and dimethylbenzene also have halogenated hydrocarbon, for example methylene dichloride, chloroform, ethylene dichloride, chlorobenzene, dichlorobenzene also has polar solvent, for example methyl-sulphoxide, tetramethylene sulfone, dimethyl formamide and N-methyl-pyrrolidone, and alcohols, methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol.
If the acid of use also can be used as thinner suitably.
The acid that is adapted at using in the inventive method (C) is all inorganic and organic acids, haloid acid for example, and sulfuric acid, alkyl-, aryl-and haloalkyl sulfonic acid, particularly haloalkyl carboxylic acid, for example trifluoroacetic acid.
When carrying out the inventive method (C), temperature of reaction can change in sizable scope.Generally speaking, be reflected under the temperature between 0 ℃ and 250 ℃, preferably under the temperature between 50 ℃ and 150 ℃, carry out.
The inventive method (C) is generally under atmospheric pressure carried out.
When carrying out the inventive method (C), the reacted constituent of formula (IV) and acid are generally used with for example equimolar amount.If but suitably also can use this acid as solvent or as catalyzer.
Method (D α) is characterised in that, if if suitably in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the carboxylic acid halide of formula V separately.
Being adapted at according to the thinner that uses in the inventive method (D α) is that all are to acyl halide inert solvent.The preferred hydro carbons that uses, gasoline for example, benzene, toluene, dimethylbenzene and 1,2,3,4-tetralin, also has halohydrocarbon, methylene dichloride for example, chloroform, tetracol phenixin, chlorobenzene and neighbour-dichlorobenzene also have ketone, for example acetone and methyl isopropyl Ketone, nitrile, acetonitrile for example also has ethers, Anaesthetie Ether for example, and tetrahydrofuran (THF) is with diox, also have carboxylicesters, for example ethyl acetate also has intensive polar solvent, for example methyl-sulphoxide and tetramethylene sulfone.If the stability to hydrolysis of acyl halide allows, reaction can also be carried out in the presence of water.
The suitable acid binding agent that is used for the inventive method (D α) reaction is the conventional acid acceptor.The preferred tertiary amines of using, triethylamine for example, pyridine, diazabicyclo octane (DABCO), diazabicyclo hendecene (DBU), diazabicyclo-nonene (DBN), H ü nig alkali and N, N-dimethyl-aniline also has alkaline earth metal oxide, for example magnesium oxide and calcium oxide, also have basic metal and alkaline earth metal carbonate, yellow soda ash for example, salt of wormwood and lime carbonate, also has alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide.
When carrying out the inventive method (D α), temperature of reaction can change in sizable scope.Generally speaking, be reflected at-20 ℃ and+temperature between 150 ℃ under, preferably under the temperature between 0 ℃ and 100 ℃, carry out.
When carrying out the inventive method (D α), the initiator of formula (I-1-a) to (I-3-a) and the carbonylic halide of formula V generally use with about equimolar amount separately.But also can use big relatively excessive (maximum 5 moles) carbonylic halide.Carry out aftertreatment by ordinary method.
Method (D β) is characterised in that, if if suitably in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the carboxylic acid anhydride of formula (VI) separately.
Being adapted at according to the thinner that uses in the inventive method (D β) preferably also is preferred those thinners when using acyl halide.The carboxylic acid anhydride of excessive use can also work as thinner simultaneously in addition.
The acid binding agent that randomly adds in method (D β) preferably also is preferred those acid binding agents when using acyl halide.
The temperature of reaction of carrying out the inventive method (D β) can change in sizable scope.Generally speaking, be reflected at-20 ℃ and+temperature between 150 ℃ under, preferably under the temperature between 0 ℃ and 100 ℃, carry out.
When carrying out the inventive method (D β), the initiator of formula (I-1-a) to (I-3-a) and the carboxylic acid anhydride of formula (VI) are generally used with about equimolar amount separately.But also can use big relatively excessive (maximum 5 moles) carboxylic acid anhydride.Carry out aftertreatment by ordinary method.
Generally speaking, by distillation or by removing the thinner and the carboxylic acid anhydride of excessive existence with organic solvent or water, and the carboxylic acid that generates.
Method (E) is characterised in that, if if suitably in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the chloro-formic ester or the chloroformic acid mercaptan ester of formula (VII) separately.
The acid binding agent that is fit to the inventive method (E) is all conventional acid acceptors.The preferred tertiary amines of using, triethylamine for example, pyridine, DABCO, DBU, DBA, H ü nig alkali and N, N-dimethyl-aniline also has alkaline earth metal oxide, for example magnesium oxide and calcium oxide, also have basic metal and alkaline earth metal carbonate, yellow soda ash for example, salt of wormwood and lime carbonate, also has alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide.
The suitable diluent of using in according to the inventive method (E) is that all are to chloro-formic ester or chloroformic acid thioesters inert solvent.The preferred hydro carbons that uses, gasoline for example, benzene, toluene, dimethylbenzene and 1,2,3,4-tetralin, also has halohydrocarbon, methylene dichloride for example, chloroform, tetracol phenixin, chlorobenzene and neighbour-dichlorobenzene also have ketone, for example acetone and methyl isopropyl Ketone, nitrile, acetonitrile for example also has ethers, Anaesthetie Ether for example, and tetrahydrofuran (THF) is with diox, also have carboxylicesters, for example ethyl acetate also has intensive polar solvent, for example methyl-sulphoxide and tetramethylene sulfone.
When carrying out the inventive method (E), temperature of reaction can change in sizable scope.Carry out under existing if be reflected at thinner and acid binding agent, temperature of reaction generally-20 ℃ and+100 ℃ between, preferably between 0 ℃ and 50 ℃.
The inventive method (E) is generally under atmospheric pressure carried out.
When carrying out the inventive method (E), the initiator of formula (I-1-a) to (I-3-a) and the suitable chloro-formic ester of formula (VII) or chloroformic acid thioesters generally use with about equimolar amount separately.But also can use one or another kind of composition of big relatively excessive (maximum 2 moles).Carry out aftertreatment by ordinary method.Generally speaking, remove sedimentary salt, and remove the reaction mixture that thinner comes concentrating residues by reducing pressure down.
The inventive method (F) is characterised in that, if in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the compound of formula (VIII) separately.
In preparation method (F), 0 ℃ under 120 ℃, preferably 20 ℃ under 60 ℃, for the initiator of every mole of formula (I-a) to (I-3-a), use the chloro monothio manthanoate of about 1 mole of formula (VIII) or chloro dithio formate to react.
If suitably, the thinner that can add is all inertia polar organic solvents, ethers for example, and nitrile, ketone, carboxylicesters, amides, sulfone, sulfoxide also has halogenated alkane.
Preferred methyl-sulphoxide, tetrahydrofuran (THF), ethyl acetate, dimethyl formamide or the methylene dichloride of using.
In a preferred embodiment, if by add strong proton-removed agent for example sodium hydride or potassium tert.-butoxide prepare the enolate of compound (I-1-a) to (I-3-a), then can save other adding acid binding agent.
If the use acid binding agent, then conventional inorganic or organic bases is suitable, and the example that can mention is a sodium hydroxide, yellow soda ash, salt of wormwood, pyridine, triethylamine.
This reaction can or add at normal atmosphere to depress to be carried out, and preferably under atmospheric pressure carries out.Carry out aftertreatment by ordinary method.
The inventive method (G) is characterised in that, if if suitably in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the SULPHURYL CHLORIDE of formula (IX) separately.
In preparation method (G) ,-20 ℃ under 150 ℃, preferably 20 ℃ under 70 ℃, for the initiator of every mole of formula (I-1-a) to (I-3-a), use the SULPHURYL CHLORIDE of about 1 mole of formula (IX) to react.
If suitably, the thinner that can add is all inertia polar organic solvents, ethers for example, amides, ketone, carboxylicesters, nitrile, sulfone, sulfoxide or halohydrocarbon, for example methylene dichloride.
Preferred methyl-sulphoxide, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dimethyl formamide or the methylene dichloride of using.
In a preferred embodiment, if by add strong proton-removed agent for example sodium hydride or potassium tert.-butoxide prepare the enolate of compound (I-1-a) to (I-3-a), then can save other adding acid binding agent.
If the use acid binding agent, then conventional inorganic or organic bases is suitable, and the example that can mention is a sodium hydroxide, yellow soda ash, salt of wormwood, pyridine, triethylamine.
This reaction can or add at normal atmosphere to depress to be carried out, and preferably under atmospheric pressure carries out.Carry out aftertreatment by ordinary method.
The inventive method (H) is characterised in that, if if suitably in the presence of the thinner and suitably in the presence of acid binding agent, the compound of formula (I-1-a) to (I-3-a) reacts with the phosphorus compound of formula (X) separately.
In preparation method (H), under the temperature between-40 ℃ to 150 ℃, preferably under the temperature between-10 ℃ to 110 ℃, for every mole compound (I-1-a) to (I-3-a), use 1-2, the phosphorus compound of preferred 1-1.3 mole formula (X) obtains the compound of formula (I-1-e) to (1-3-e).
If suitably, the thinner that can add is all inertia polar organic solvents, ethers for example, amides, ketone, carboxylicesters, nitrile, alcohols, sulfide, sulfone, sulfoxide or the like.
Preferred acetonitrile, methyl-sulphoxide, ethyl acetate, tetrahydrofuran (THF), dimethyl formamide or the methylene dichloride of using.
If suitably, operable acid binding agent is conventional inorganic or organic bases such as oxyhydroxide, carbonate or amine.Example has sodium hydroxide, yellow soda ash, salt of wormwood, pyridine, triethylamine.
This reaction can or add at normal atmosphere to depress to be carried out, and preferably under atmospheric pressure carries out.Carry out aftertreatment by the organic chemistry ordinary method.The end product that obtains is preferably by crystallization, chromatogram purification or by being referred to as " initial stage distillation " (i.e. volatile component is removed in decompression down) purifying.
Method (I) is characterised in that, if suitably in the presence of thinner, and the reaction of the amine of the compound of formula (I-1-a) to (I-3-a) and the metal hydroxides of formula (XI) or metal alkoxide or formula (XII).
The preferable absorbent that is used for the inventive method (I) is an ethers, tetrahydrofuran (THF) ， diox for example, and Anaesthetie Ether or also have alcohols, methyl alcohol for example, ethanol, Virahol also has water.
The inventive method (I) is generally under atmospheric pressure carried out.Temperature of reaction is generally between-20 ℃ and 100 ℃, preferably between 0 ℃ and 50 ℃.
The inventive method (J) is characterised in that, the compound of formula (I-1-a) to (I-3-a) separately (J α) if if suitably in the presence of the thinner and suitably in the presence of catalyzer, compound reaction with formula (XIII), perhaps (J β) is if if suitably in the presence of thinner and suitably in the presence of acid binding agent, with the compound reaction of formula (XIV).
In preparation method (J α), 0 ℃ under 100 ℃, preferably 20 ℃ under 50 ℃, for the initiator of every mole of formula (I-1-a) to (I-3-a), use the isocyanic ester of about 1 mole of formula (XIII) to react.
If suitably, the thinner that can add is all inertia polar organic solvents, ethers for example, amides, nitrile, ketone, carboxylicesters, sulfone, sulfoxide.
Promote reaction if suitably, can add catalyzer.The catalyzer that can add is an organo-tin compound highly beneficially, for example dibutyl tin laurate.Reaction is preferably under atmospheric pressure carried out.
In preparation method (J β), 0 ℃ under 150 ℃, preferably 20 ℃ under 70 ℃, for the initiator of every mole of formula (I-1-a) to (I-3-a), use the urea chloride of about 1 mole of formula (XIV) to react.
The thinner that can add is all inertia polar organic solvents, for example ethers, amides, ketone, carboxylicesters, sulfone, sulfoxide or halohydrocarbon if suitably.
Preferred methyl-sulphoxide, tetrahydrofuran (THF), ethyl acetate, dimethyl formamide or the methylene dichloride of using.
In a preferred embodiment, if by add strong proton-removed agent for example sodium hydride or potassium tert.-butoxide prepare the enolate of compound (I-1-a) to (I-3-a), then can save other adding acid binding agent.
If the use acid binding agent, then conventional inorganic or organic bases is suitable, and the example that can mention is a sodium hydroxide, yellow soda ash, salt of wormwood, triethylamine or pyridine.
This reaction can or add at normal atmosphere to depress to be carried out, and preferably under atmospheric pressure carries out.Carry out aftertreatment by ordinary method.
Active compound of the present invention is fit to the control animal pest, preferred arthropods and nematode, particularly agricultural, and forest stores insect and Arachnida that product and material protection and health field ran into.It all is activated to responsive and resistance species generally, and all or some stage of anti-growth.Above-mentioned insect comprises: Isopoda (Isopoda), Oniscus asellus for example, pillworm (Armadillidiumvulgare) and Porcellio scaber; Polypody detailed outline (Diplopoda), for example Blaniulus gutttulatus; Chcilopoda order (Chilopoda), for example Geophilus carpophagus and cricket Yan order kind (Scutigera spec.); Comprehensive detailed outline (Symphyla), for example Scutigerella immaculata; Thysanura (Thysanura), for example silverfiss (Lepisma saccharina); Collembola (Collembola), for example Onychiurus armatus; Orthoptera (Orthoptera), the non-Lian in east (Blatta orientalis) for example, periplaneta americana (Periplaneta americana), the non-Lian in Madeira (Leucophaea maderae), Groton bug (Blattella germanica), house cricket found in a kitchen (Acheta domesticus), Gryllotalpa spp (Gryllotalpa spp.), torrid zone migratory locusts (Locusta migratoriamigratorioides), long volume is born locust (Melanoplus differentialis) and Schistocerca gregaria; Dermaptera (Dermaptera), for example European earwig (Forficula auricularia); Isoptera (Isoptera), for example Cryptotermes (Reticulitermes spp.); Anoplura (Anoplura), grape phylloxera (Phylloxera vastatrix) for example, woolly aphid belongs to (Pemphigus spp.), head louse (Pediculus humanus corporis), and blind lice belongs to (Haematopinus spp.) and long volume lice (Linognathus spp.); Mallophaga (Mallophaga), for example Trichodectes (Trichodectes spp.) and Damalinea spp.; Thysanoptera (Thysanoptera), for example greenhouse Hercinothrips spp (Hercinothrips femoralis) and cotton thrips (Thrips tabaci); Heteroptera (Heteroptera), for example brown scutteleerid belongs to (Eurygasterspp.), Dysdercus intermedius, and beet is intended lace bug (Piesma quadrata), bedbug (Cimex lectularius), Rhodnius prolixus and triatoma sanguisuga belong to (Triatoma spp.); Homoptera (Homoptera), Aleurodes brassicae for example, whitefly in bt cotton (Bemisiatabaci), Trialeurodes vaporariorum Westwood (Trialeurodes vaporariorum), cotten aphid (Aphisgossypii), brevicoryne brassicae (Brevicoryne brassicae), the tea deer conceals knurl volume aphid (Cryptomyzus ribis), black bean aphid (Aphis fabae), Doralis pomi, eriosoma lanigerum (Eriosoma lanigerum), mealy plum aphid (Hyalopterus arundinis), Macrosiphum avenae, knurl volume aphid (Myzus spp.), hops knurl volume aphid (Phorodonhumuli), grain Rhopalosiphum spp (Rhopasiphum padi), leafhopper belongs to (Empoasca spp.), Euscelis bilobatus, rice green leafhopper (Nephotettix cincticeps), brown apricot scale (Lecanium corni), Fructus oleae europaeae helmet (Saissetia oleae), rice small brown rice planthopper (Laodelphax striatellus), brown back rice plant hopper (Nilaparvata lugens), California red scale (Aonidiella aurantii), Aspidiotus hederae, mealybug belongs to (Pseudococcus spp.) and Psylla spp (Psylla spp.); Lepidopteran (Lepidoptera), for example, pink bollworm (Pectinophora gossypiella), loose looper (Bupalus piniarius), Cheimatobia brumata, Lithocolletis blancardella, cherry ermine moth (Hyponomeuta padella), small cabbage moth (Plutella maculipennis), tent caterpillar (Malacosoma neustria), Euproctis chrysorrhoea, Euproctis (Lymantria spp.), cotton shot hole of leaf lyonetid (Bucculatrix thurberiella), Phyllocnisti citrella, cutworm (Agrotis spp.), cutworm (Euxoa spp.), brown noctuid (Feltia spp.), earias insulana (Earias insulana), Noctua (Heliothis spp.), beet armyworm (Spodoptera exigua), lopper worm (Mamestra brassicae), Panolisflammea, prodenia litura (Prodenia litura), Noctua (Spodoptera spp.), cabbage looper (Trichoplusia ni), carpocapsa pononella (Carpocapsa pomonella), Pier (Pieris spp.), snout moth's larva (Chilo spp.), Pyrausta nubilalis, Ephestia kuehniella, rheum officinale snout moth's larva (Galleria mellonella), bag casemaking clothes moth (Tineola bisselliella), etting moth (Tinea pellionella), brown oecophorid (Hofmannophila pseudospretella), Cacoecia podana, Capuareticulana, choristoneura fumigerana (Choristoneura fumiferana), grape codling moth (Clysia ambiguella) (Clysia ambiguella), tea yellow leaf curl moth (Homona magnanima) and the green leaf roller of oak (Tortrix viridana); Coleoptera (Coleoptera), for example, furniture death watch beetle (Anobium punctatum), Rhizopertha dominica, bean weevil (Acanthoscelides obtectus), house longhorn beetle (Hylotrupes bajulus), Agelastica alni, first bell potato beetle (Leptinotarsa decemlineata), Phaedon cochleariae, chrysomelid genus (Diabrotica spp.), the blue flea beetle (Psylliodes chrysocephala) of rape, mexican bean ladybird (Epilachna varivestis), Atomaria spp., saw chest ostomatid (Oryzaephilus surinamens), weevil belongs to (Anthonomus spp.), Sitophilus (Sitophilus spp.), Otiorrhynchus sulcatus, banana spider base weevil (Cosmopolites sordidus), Ceuthorrhynchus assimilis, lucerne place leaf weevil (Hypera posttica), khapra beetle belongs to (Dermestes spp.), khapra beetle belongs to (Trogoderma spp.), khapra beetle belongs to (Anthrenus spp.), attagenus piceus (Attagenuespp.), powder moth (Lyctus spp.), Meligethes aeneus, Ptinus (Ptinusspp.), golden yellow ptinid (Niptus hdoleucus), wheat ptinid (Gibbium psylliodes), intend paddy Oryza (Tribolium spp.), bloom first (Tenebrio molitor), click beetle belongs to (Agriotes spp.), acupuncture needle Eimeria (Conoderus spp.), Melolonthameiolontha, chafer in June (Amphimallon solstitialis) and Costelytra zealandica; The film wing belongs to (Hymenoptera), and for example Neodiprion spp belongs to (Diprion spp.), tenthredinidae (Hoplocampa app.), ant (Lasius spp.), kitchen ant (Monomoriumpharaonis), and wasp (Vespa spp.); Dipteron belongs to (Diptera), for example, squeak mosquito (Aedes spp.), spot Anopheles (Anophelesspp.), culex (Culex spp.), drosophila yellow gorilla (Drosophila melanogaster), housefly (Musca spp.), stable fly (Fannia spp.), calliphora erythrocephala (Calliphoraerythrocephala), lucilia sericata (Lucilia spp.), Chrysomyia spp., cuterbrid belongs to (Cuterebra spp.), Gastrophilus spp., Hyppobosca spp., Genus Stomoxys (Stomoxys spp.), the nose fly belongs to (Oestrus spp.), Hypoderma (Hydodermaspp.), the gadfly belongs to (Tabanus spp.), Tannia spp., Bibio hortulanus, Sweden's wheat stem chloropid fly (Oscinella frit), wheat fly (Phorbia spp.), beet fly (Pegomyia hyoscyami), Mediterranean fruitfly (Ceratitis capitata), dacus oleae (Dacus oleae) and European daddy-longlegs (Tipula paludosa); Siphonaptera (Siphonaptera), for example, Xenopsyllacheopis (Xenopsylla cheopis) and Ceratophyllus (Ceratophyllus spp.); Arachnida (Arachnida), for example Scopio maurus and black widow (Latrodectus mactans); Acarina (Acarina), for example, Acarus siro (Acarus siro), latent beak ant (Argasspp.), the beak tick belongs to (Ornithodoros spp.), Dermanyssus gallinae (Dermanyssusgallinae), Eriophyes ribis, citrus rust mite (Phyllocoptruta oleivora), Boophilus (Boophilus spp.), carrapato belongs to (Rhipicephalus spp.), Amblyomma (Amblyomma spp.), Hyalomma spp., hard ant (Ixodes spp.), the rice weevil mite belongs to (Psoroptes spp.), Trombidium (Chorioptes spp.), itch mite (Sarcoptesspp.), the line mite belongs to (Tarsonemus spp.), lucerne place tongue mite (Bryobia praetiosa), red spider (Panonychus spp.) and tetranychus telarius belong to (Tetranychus spp.).
The outstanding part of The compounds of this invention is high insect and the acaricidal activity of killing.
Active compound of the present invention especially successfully is applied to the deleterious insect of plant, for example larva of horseradish ape chrysomelid (Phaedon cochleariae) or the larva of rice green leafhopper (Nephotettiix cincticeps) extremely extremely kill black peach aphid (Myzus persicae) or also kill European red mite (Panonychus ulmi).
Active compound of the present invention can also be used as defoliating agent, and siccative kills the straw agent, particularly as killing the weeds agent.In a broad sense, so-called weeds are all plants of the place growth do not expected at it by understanding.Material of the present invention is the amount that depends primarily on use as steriland herbicide or selective herbicide.
For example, relevant with following plant, can use active compound of the present invention: the broadleaf weed kind: mustard belongs to (Sinapis), separate row Vegetable spp (Lepidium), Bedstraw (Galium), Stellaria (Stellaria), Matricaria (Matricaria), Anthemis (Anthemis), Herba galinsogae parviflorae (Galinsoga), Chenopodium (Chenopodium), Urtica (Urtica), Senecio (Senecio), Amaranthus (Amaranthus), Portulaca (Portulaca), Xanthium (Xanthium), japanese bearbind belongs to (Convolvulus), sweet potato genus (Ipomoea), Polygonum (Polygonum), sesbania (Sesbania), Ambrosia (Ambrosia), Cirsium (Cirsium), bristlethistle (Carduus), sonchus L (Sonchus), Solanum (Solanum), weldering Lepidium (Rorippa), Leaf of Chinese Deciduous Cypress belongs to (Rotala), Vandellia (Lindernia), wild awns fiber crops belong to (Lamium), Veronica (Veronica), abutilon (Abutilon), bur (Emex), Datura (Datura), Viola (Viola), the weasel hemp nettle belongs to (Galeopsis), papaver (Papaver), bachelor's-button (Centaurea), Clover (Trifolium), Ranunculus (Ranunculus) and Dandelion (Taraxacum).Dicotyledonous crops kind: Gossypium (Gossypium), Glycine (Glycine), Beta, Daucus (Daucus), Phaseolus (Phaseolus), Pisum, Solanum (Solanum), linum (Linum), sweet potato genus (Ipomoea), vetch (Vicia), Nicotiana (Nicotiana), tomato belongs to (Lycopersicon), peanut (Arachis), mustard belongs to (Brassica), Lactuca (Lactuca), Cucumis (Cucumis) and buffalo gourd (Cucurbita).Monocotyledon weed kind: Echinochloa (Echinochloa), setaria (Setaria), Panicum (Panicum), knotgrass (Digitaria), ladder is herded genus (Phleum), annual bluegrass belongs to (Poa), festuca (Festuca), cricket Lepidium (Eleusine), Brachiaria (Brachiaria), lolium (Lolium), Brome (Bromus), Avena (Avena), Cyperus (Cyperus), Sorghum (Sorghum), Agropyron (Agropyron), Cycnodon, Monochoria (Monchoria), genus fimbristylis (Fimbristylis), arrowhead (Sagittaria), Eleocharis (Eleocharis), bit of a bridle grass (Scirpus), Dallis grass (Paspalum), Ischaemum, cusp Pittosporum (Sphenoclea), talon eria (Dactyloctenium), cut gang Ying and belong to (Agrostis), amur foxtail belongs to (Alopecurus), and Apera.Monocot crops kind: Oryza (Oryza), Zea (Zea), Triticum (Triticum), Hordeum (Hordeum), Avena (Avena), Secale (Secale), Sorghum (Sorghum), Panicum (Panicum), sugarcane (Saccharum), pineapple (Ananas), Asparagus (Asparagus) and allium (Allium).
But the purposes of active compound of the present invention is not subjected to the restriction of these kinds, but expands to other plant in an identical manner.
According to concentration, The compounds of this invention for example is suitable at industrial site and railway, is with or without on the roads of trees or the square all control weeds.These compounds are used to too in perennial plantation plant place, lawn, playground and pasture control weeds, described perennial plantation plant place is the woods for example, the tree of ornamental plantation, orchard, the vineyard, lemon garden, nut garden, banana plantation, cafetal, tea plantation, rubber plantation, oil palm plantation, cocoa plantation, mushy fruit plantation plant and hop field, and be used in year living farm crop place selective control weeds.
The compounds of this invention be particularly suitable for before bud and bud after, selective control monocotyledon weed in dicotyledonous farm crop.For example they can be used for preventing and treating the injurious weed of cotton or beet like a bomb.
Active compound can be mixed with conventional formulation, for example solution, emulsion, wettable powder, suspension agent, pulvis, pulvis subtilis, paste, soluble powder, granule, suspendible missible oil, be soaked with the natural and synthetic material of active compound and be wrapped in trickle capsule in the polymkeric substance.
These type agent are produced in a known manner, for example, and by being that liquid solvent solvent and/or solid carrier mix with expanding agent with active compound, and optional use tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or pore forming material.
If the expansion agent of using is a water, then also can use-case such as organic solvent make solubility promoter.Suitable liquid solvent mainly contains: aromatics, and as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatic compound and chlorinated aliphatic hydrocarbon are as chlorinated benzene class, polyvinyl chloride-base or methylene dichloride, fat hydrocarbon, as hexanaphthene or paraffin, mineral oil fraction for example, mineral oil and vegetables oil, alcohols, as butanols or ethylene glycol with and ether and ester, ketone, as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide and methyl-sulphoxide, and water.
Suitable solid carrier is:
For example ammonium salt and ground natural mineral matter are as kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite and ground synthetic mineral matter, as high dispersive silicon-dioxide, alumina and silicate; The solid carrier that is fit to that is used for granule has: for example crushing and broken natural mineral matter such as calcite, marble, float stone, sepiolite and rhombspar, and the synthetic particle of organic and inorganic powder and following organic particle: for example wood sawdust, coconut husk, corn cob and tobacco stem; Suitable emulsifying agent and/or pore forming material have: for example nonionic and anionic emulsifier, as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example, alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolysate; Suitable dispersion agent has: for example, and lignin sulfite waste liquor and methylcellulose gum.
In the preparation, can use tackiness agent, as the natural and synthetic polymer of carboxymethyl cellulose and powdery, particle or latex form, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid.Other additive can be mineral oil and vegetables oil.
Also can use dyestuff, as mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye are as the salt of alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff and micro-nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Generally speaking, preparation contains the active compound of 0.1-95% weight, preferred 0.5-90%.
Active compound of the present invention can be sold that preparation exists and existed by the type of service of these formulation preparation with its merchant, as with the mixture of other active compound, described other active compound is for example insecticide, attractive substance, sterilizing agent, miticide, nematocides, mycocide, growth regulator or weedicide.Insecticide comprises for example phosphoric acid ester, carbamate, carboxylicesters, hydrochloric ether, phenylurea and the material by microorganism preparation or the like.
Useful especially mixes conjugate is for example as follows:
Mycocide:
The 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6 '-two bromo-2-methyl-4 '-trifluoromethoxy-4 '-trifluoromethyl-l, 3-thiazole-5-formylaniline; 2,6-two chloro-N-(4-trifluoromethyl benzyl) benzamide; (E)-2-methoxyl group imido grpup-N-methyl-2-(2-Phenoxyphenyl)-ethanamide; Oxine vitriol; (E)-2-{2-[6-(2-cyano-benzene oxygen)-pyrimidine-4-base oxygen base]-phenyl }-the 3-methoxy-methyl acrylate; (E)-methoxyl group imido grpup [α-(o-tolyl oxygen base)-neighbour-tolyl] methyl acetate; 2-phenylphenol (OPP), aldimorph, ammonia third phosphoric acid, anilazine, penta ring azoles,
M 9834, adjacent iodoxy aniline, F-1991, Niagara 9044, biphenyl, Bitertanol, miewensu, bromuconazole, bupirimate, the fourth Saite,
Lime sulfur mixture, Difolatan, Vancide 89, derosal, carboxin, chinomethionate, chloroneb, trichloronitromethane, hundred bacterium disappear, chlozolinate, maneb, frost urine cyanogen, cyproconazole, cyprofuram,
Dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, the mould Wei ， of second Difenoconazole, the phonetic fen of diformazan, the olefin(e) acid morpholine, alkene azoles alcohol, dinitrocrotonate, pentanoic, pyrrole bacterium sulphur, ditalimfos, the Delan, dodine ， An azolactone,
Hinosan, epoxyconazole, the phonetic phenol of second, etridiazole
Fenarimol, fenbuconazole, first furan anilide is planted the clothing ester, fenpiclonil, fenpropidin, fenpropimorph, triphenyl tin acetate, fentin hydroxide, Karbam Black, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, fluzilazol, flusulfamide, fultolanil, flutriafol, Phaltan, phosethyl Al, phthalide, fuberidazole, furalaxyl, seed dressing amine
Seed-grain is fixed,
Perchlorobenzene, own azoles Chun ， hymexazo,
Press down mould azoles, the acid amides azoles, bivalve acetate, iprobenfos (IBP), RP-26019, isoprothiolane,
Kasugamycin, copper agent, for example: copper hydroxide, copper naphthenate, COPPER OXYCHLORIDE 37,5, copper sulfate, cupric oxide, copper 8-quinolinolate and Bordeaux mixture,
Mancopper, maneb, zinc manganese ethylenebisdithiocarbamate, mepanipyrim, mebenil, metaxanin, metconazole, methasulfocarb, methuroxam, Carbatene, metsulfovax, nitrile bacterium azoles,
Nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
The spirit of fenfuram ， Evil frost, oxamocarb, oxycarboxin,
Pefurazoate, Topaze, pencycuron, rice blast phosphorus, phthalide, myprozine, disease is spent spirit, polyurethane(s), Polyoxin, the sick isothiazole of alkene, delicious peace, procymidone, propionic acid amide encircles third azoles, zinc 1,2-propylene bisdithiocarbamate, the phonetic phosphorus of pyrrole, pyrifenox, pyrimethanil, pyroquilon,
Quintozene (PCNB),
Sulphur and sulphur preparation,
Tebuconazole, tecloftalam, tecnazene, the phonetic azoles of fluorine, thiabendazole, thicyofen, thiophanate_methyl, thiram, tolclofosmethyl, methyl fluoride sulfanilamide (SN), triazolone, triadimenol, azoles bacterium piperazine, poplar bacterium amine, tricyclazole, tridemorph, fluorine bacterium azoles, triforine, triticonazole,
Validamycin, Vinclozoline,
Zineb, ziram.
Bactericide:
Bronopol, dichlorophen, chloromethylpyridine, nickel dimethyldithiocarbamate, kasugamycin, isothiazolones, furancarboxylic acid, oxytetracycline, different third thiazole of alkene, Streptomycin sulphate, tecloftalam, copper sulfate and other copper agent.
Insecticide/miticide/nematocides:
Avermectin, acephate, Acetamiprid, fluorine ester chrysanthemum ester, alanycarb, aldicarb, the oxygen aldicarb, and the nail body Cypermethrin (Alpha-cypermethrin, Alphamethrin), two worm amidines, avermectin, AZ60541, azadirachtin, Jia Ji Bi Evil phosphorus, azinphos-A, azinphos-methyl, azocyclotin
Japanese beetle genus bacillus (Bacillus popilliae), Bacillus sphaericus (Bacillus sphaericus), subtilis (Bacillus subtilis), Bacillus thuringiensis, Baculoviren, silkworm muscardine (Beauveria bassiana), beauveria tenella (Beauveria tenella) ， Evil worm prestige, benfuracarb, bensultap, benzoximate, cyfloxylate, Bifenazate, bifenthrin, Bioethanomethrin, biopermethrin, BPMC, brofenprosA, bromofos, bufencarb, Buprofezin, butocarboxim, butylpyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, fourth sulphur hectogram prestige, cartap, Chloethocarb Chlorethoxyfos, Chlorfenapyr, Zaprawa enolofos, UC 62644, chlormephos, Chlorpyrifos 94, chlorpyrifos_methyl, Chlovaporthrin, cis-resmethrin, clocythrin, cloethocarb, four mite piperazines, cynock, Cycloprene, cycloprothrin, cyfloxylate-β, cyhalothrin, cyhexatin, Cypermethrin, fly eradication amine
Deltamethrin, Systox-M, Systox-S, demeton_S_methyl, diacloden kills mite sulphur and swells, diazinon, SD-1750, TH-6040, Rogor, the luxuriant ether of dimethylvinphos ， Evil, thiodemeton, sulphonyl fourth two sufferings, benzene oxycetylene mite,
Hinosan, emamectin, Prallethrin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, Entomopfthora spp., esfenvalerate, ethiofencarb, Nialate, ethoprophos, Etofenprox, ether chrysanthemum ester, etrimfos,
Worm amine phosphorus, fenazaquin, fenbutatin oxide, fenitrothion 95, fenobucarb, fenothiocarb, Fenoxacrim, ABG-6215, Cypermethrin, fenpyrad, Fenpyrithrin, azoles mite ester, fenvalerate, fipronil, fluorine is decided amine, Fluazuron, Flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, Flutenzine, taufluvalinate, N-2790, fosmethilan, lythidathion, fubfenprox, furathiocarb
Granulosis?viruses，
Halofenozide, HCH, heptenopos, fluorine bell urea, hexythiazox, hydroprene,
Provado, isazofos, isofenphos ， oxazole phosphorus, ivermectin,
Nuclear?polyhedrosis?viruses，
Cyhalothrin, lufenuron,
The Malathion, mecarbam, Phosdrin, mesulfenphos, Metharhiziumanisopliae, Metharhizium flavoviride, Halizan, methacrifos, acephatemet, methidathion, methiocarb, methomyl, meta-tolyl-N-methylcarbamate (MTMC), milbemectin, monocrotophos,
Naled, nitenpyram, Nithiazine, Novaluron,
Omethoate, oxamyl, oxydemeton-methyl,
Paecilomyces fumosoroseus (Paecilomyces fumosoroseus), thiophos-A, thiophos-M, permethrin, Tsidial, phorate, Phosalone, R-1504, phosphamidon, Volaton, anti-bud prestige, pririmiphos_methyl, Pyrimithate-A, Pyrimithate-M, Profenofos, promecarb, Kayaphos, Propoxur, Toyodan, Fac, pymetrozine, pyraclofos, pyresmethrin, pyrethrin, pyridaben, Pyridathion, pyrimidifen, pyriproxyfen
Resitox,
Ribavirin，
Dioxabenzofos, sebufos, silafluofen, Spinosad controls snout moth's larva sulphur phosphorus, the first Toyodan,
Taufluvalinate, tebufenozid, tebufenpyrad, tebupirimiphos, fluometuron, tefluthrin, temephos, spy's prestige of going out, Terbufos, tetrachlorvinphos, theta-cypermethrin, moth fly nitrile, Thiatriphos, Thiocyclam hydrogenoxalate, the two prestige of sulphur, monocrotophos, thuringiensin, thiometon, thionazin, tralomethrin, benzene thiophene mite, triazophos, triazuron, Trichlophenidine, Trichlorphon, desinsection is grand, dimethacarb
Bud goes out many, Vaniliprole, and Verticillium lecanii,
YI5302，
zeta-cypermethrin，Zolaprofos，
(1R-cis)-[5-(phenyl methyl)-3-furyl]-methyl-3-[(dihydro-2-oxo--3 (2H)-furylidene)-and methyl]-2,2-dimethyl cyclopropane carboxylic acid ester,
(3-Phenoxyphenyl)-methyl-2,2,3, the 3-4-methyl cyclopropane carboxylic acid ester,
1-[(2-chloro-5-thiazolyl) methyl] tetrahydrochysene-3,5-dimethyl-N-nitro-1,3,5-triazines-2 (1H)-imines,
2-(2-chloro-6-fluoro phenyl)-4-[4-(1, the 1-dimethyl ethyl) phenyl]-4,5-dihydro-oxazole,
2-(acetoxyl group)-3-dodecyl-1, the 4-naphthalenedione,
2-chloro-N-[[[4-(1-phenyl ethoxy) phenyl]-amino]-carbonyl]-benzamide,
2-chloro-N-[[[4-(2,2-two chloro-1,1-difluoroethoxy) phenyl]-amino]-carbonyl]-benzamide,
Carboxylamine 3-aminomethyl phenyl propyl ester,
4-[4-(4-ethoxyl phenenyl)-4-methyl amyl]-1-fluoro-2-phenoxy group-benzene,
4-chloro-2-(1, the 1-dimethyl ethyl)-5-[[2-(2,6-dimethyl-4-phenoxy group phenoxy group) ethyl] sulfenyl]-3 (2H)-pyridazinones,
4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl) methoxyl group]-3 (2H)-pyridazinones,
4-chloro-5-[(6-chloro-3-pyridyl) methoxyl group]-2-(3, the 4-dichlorophenyl)-3 (2H)-pyridazinones,
Bacillus thuringiensis bacterial strain EG-2348,
Phenylformic acid [2-benzoyl-1-(1, the 1-dimethyl ethyl)-hydrazine,
Butyric acid 2,2-dimethyl-3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4,5] dodecane-3-alkene-4-ester,
[3-[(6-chloro-3-pyridyl) methyl]-the inferior thiazolidyl of 2-]-cyanamide,
Dihydro-2-(Nitromethylene)-2H-1,3-thiazine-3 (4H)-formaldehyde,
[2-[[1,6-dihydro-6-oxo-1-(phenyl methyl)-4-pyridazinyl] oxygen base] ethyl]-urethanum,
N-(3,4,4-three fluoro-1-oxo-3-butenyls)-glycine,
N-(4-chloro-phenyl-)-3-[4-(difluoro-methoxy) phenyl]-4,5-dihydro-4-phenyl-1H-pyrazoles-1-methane amide,
N-[(2-chloro-5-thiazolyl) methyl]-N '-methyl-N "-nitro-guanidine,
N-methyl-N '-(1-methyl-2-propenyl)-1,2-hydrazine two (thioformamide),
N-methyl-N '-2-propenyl-1,2-hydrazine two (thioformamide),
O, O-diethyl [2-(dipropyl amino)-2-oxoethyl]-ethylamino thiophosphatephosphorothioate.
Weedicide:
For example N-anilide, for example diflufenican and Stam F-34; The aryl carboxylic acid class, lontrel for example, dicamba 98 and picloram; Aryloxy alkane acids, for example 2,4-drips, and 2, the 4-Embutox, 2,4-drips propionic acid, fluroxypyr, 2 first, 4 chlorine, Vi par and TRICLOPYR ACID; Aryloxy phenoxy alkane acid ester class, diclofop-methyl ， oxazole diclofop-methyl for example, fluazifop, standing grain spirit of pyrrole fluorine chlorine and quizalofop; Azine ketone, for example pyrazon and norflurazon; Amino formate, Y 3 for example, desmedipham, phenmedipham and propham; Chloro monoacetylaniline class, alachlor for example, second grass peace, butachlor, pyrrole grass peace, metolachlor, third grass peace and the propachlor; Dinitrobenzene N-anilide, oryzalin for example, pendimethalin and trifluralin; Diphenylether, acifluorfen for example, bifenox, fluoroglycofenethyl, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, for example the chlorine wheat is grand, Diuron Tech, fluometuron, isoproturon, methoxydiuron and methabenzthiazuron; The azanol class, alloxydim for example, clethodim, benzthiazuron, sethoxydim and tralkoxydim; Imidazolone type, Imazethapyr for example, miaow grass ester, weed eradication cigarette and weed eradication quinoline; Nitrile, bromoxynil for example, Niagara 5006 and ioxynil; Oxyacetamide, for example mefenacet; Sulfonylurea, amidosulfuron for example, the benzyl ethyl methyl, chlorimuron, chlorsulfuron, ether is yellow grand, metsulfuron-methyl, nicoculsfuron, Fluoropyrimidinesulfuron, pyrazosulfuron, thiophene methyl, triasulfuron and tribenuron-methyl; Thiocarbamates, pebulate for example, weed eradication spy, oat fear, EPTC, esprocarb, Hydram, prosulfocarb, thiobencarb and triallate; Triazines, atrazine for example, cyanazine, simazine, simetryn, terbutryn and terbutylazine; Triazinone, hexazinone for example, metamitron and piperazine humulone; Other class, aminotriazole for example, benfuresate, bentazone, cinmethylin ， clomazone, clopyralid, two benzene azoles are fast, dithiopyr, ethofumesate, fluorochloridone, careless ammonium phosphine, glyphosate, isoxaben, pyridate, quinclorac, quinmerac, careless sulphur phosphorus and tridiphane.
Active compound of the present invention can also be sold that preparation exists and exists with the type of service as with the mixture of synergistic agent by these formulation preparation with its merchant.Synergistic agent is to improve the active compound effect and himself unnecessary activated compound.
The active compound content of being sold the type of service of formulation preparation by the merchant can change in wide region.The concentration of the active compound of type of service can be the 0.0000001-95% weight active compound, preferred 0.0001-1% weight.
Use these compounds with the usual manner that is suitable for these types of service.
When being used for killing health field insect and stored prod insect, these active compounds have fabulous residual effect to timber and clay, and to good stability is arranged with the alkali on the material of lime treatment.
Not only to killing plant, health field and stored prod insect have activity to active compound of the present invention, but also are used for field of veterinary, parasiticide animal (epizoa), for example hard tick, soft ticks, psoroptes equi, trombiculid, fly (sting and suck), tachinid larva, lice, head louse and flea.Such parasite comprises:
Anoplura (Anolpurida), for example, Haematopinus (Haematopinus spp.), Linognathus spp (Linognathus spp.), lice belongs to (Pediculus spp.), and Pthirus (Phtirusspp.) and pipe lice belong to (Solenopotes spp.).
Mallophaga is stung lice (Mallophagida) and Amblycerina and Ischnocerina suborder, for example the hair Trichodectes (Trimenopon spp.), Menopon spp., huge Trichodectes (Trinoton spp.), Bovicola (Bovicola spp.), Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felcolaspp..
Diptera (Diptera) and Nemocera (Nematocerina) and Brachycerina suborder, yellow-fever mosquito (Aedes spp.) for example, spot Anopheles (Anopheles spp.), culex (Culex spp.), Simulium (Simulium spp.), the true buffalo gnat of all woolen (Eusimulium spp.), sand fly (Phlebotomus spp.), Lutzomyia (Lutzomyia spp.), storehouse midge (Culicoides spp.), spot horsefly (Chrysops spp.), knurl horsefly (Hybomitra spp), Atylotus spp., Gadfly (Tabanus spp.), Chrysozona (Haematopotaspp.), Philipomyia spp., Braula spp., Musca spp., Hydrotaea (Hydrotuea spp.), sting fly (Stomoxys spp.), Haematobia spp., Morellia spp., latrine fly (Fannia spp.), Glossina spp., Calliphoraspp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., other sarcophagid (Sarcophaga spp.), Oestrus spp., torsalo (Hypoderma spp.), Gasterophilus spp., hippoboscid (Hippobosca spp.), Lipoptena spp. and Melophagus spp..
Siphonaptera (Siphonapterida), for example, flea belongs to (Pulex spp.), Ctenocephalides spp., mouse flea (Xenopsylla spp.), and c. leaf flea (Ceratophyllus spp.).
Heteroptera (Heteropterida), for example, Cimex (Cimex spp.), triatoma sanguisuga belongs to (Triatoma spp.), Rhodnius spp., and Panstrongylus (Panstrongylusspp.).
Non-Lian order (Blattarida), the non-Lian in east (Blatta orientalis) for example, periplaneta americana (Periplaneta americana), Groton bug (Blattela germanica) and non-Lian belong to (Supella spp.).
Mite subclass (Acarida) and metaspiracle order (Metastigmata) and mesostigma order (Mesostigmata), for example, latent beak tick belongs to (Argas spp.), the beak tick belongs to (Ornithodorus spp.), ear tick (Otabius spp.), hard tick (Ixodesspp.), Amblyomma (Amblyomma spp.), Boophilus (Boophilus spp.), Dermacentor (Dermacentor spp.), Haemophysalis spp., glass eye tick (Hyalommaspp.), carrapato belongs to (Rhipicephalus spp.), Dermanyssus gallinae (Dermanyssusspp.), auspicious upright tapeworm (Raillietia spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp..
Actinedida (Trombidiformes, Prostigmata) and Acaridida (Astigmata), Acarapis spp. for example, Cheyletiella (Cheyletiella spp.), Ornithocheyletia spp., Myobia spp., itch mite (Psorergates spp.), demodicid mite (Demodex spp.), trombiculid (Trombicula spp.), Listrophorusspp., Acarus siro (Acarus spp.), junket mite (Tyrophagus spp.), have a liking for wooden mite (Caloglyphus spp.), Hypodectes spp., wing clothing mite belongs to (Pterolichusspp.), trombiculid (Psoroptes spp.), trombiculid (Chorioptes spp.), Otodectes spp., itch mite (Sarcoptes spp.), Notoedres spp., foot mite (Knemidocoptes spp.,), Cytodites spp., and Laminosioptesspp..
For example they show killing the outstanding activity of boophilus microplus (Boophilus microplus) and lucilia sericata (Lucilla cuprina).
The active compound of formula of the present invention (I) also is suitable for preventing and treating the Arthropoda of infecting the agriculture production domestic animal, and described domestic animal is an ox for example, sheep, goat, horse, pig, donkey, camel, buffalo, rabbit, chicken, turkey, duck, goose and honeybee, other pet, for example dog, cat, bird of raising in cages and fish jar are cultured fish and are referred to as the animal of laboratory animal, for example hamster, cavy, rat and mouse.By preventing and treating these Arthropodas, can avoid domestic animal dead and avoid the minimizing (product is meat for example, milk, wool, leather, egg, honey etc.) of product volume, so the application of the invention active compound can be realized the nursing of more economical simpler animal.
In field of veterinary, active compound of the present invention is in a known way through enteral administration, for example with tablet, and capsule, draught, draught, granule, paste, bolus is by the form of eating method and suppository; By administered parenterally, for example pass through to inject (intramuscular, subcutaneous, intravenously, intraperitoneal etc.), imbed, by nasal administration,, spray by with for example dipping or dipping bath, the Shi Hedian that falls executes, wash with and the form skin use of dusting, also can be by means of the article of making of mould that contain active compound, neck ring for example, ear pendant, tailpiece, the bottom bands of trouser legs, halter, marker etc. and using.
When to livestock, poultry, when pets etc. are used, formula of the present invention (I) active compound can be used as the preparation (powder agent for example that contains active compound with the amount of 1-80% weight ratio, emulsion, the flowable composition) is used, directly uses or doubly back use of dilution 100-10000, perhaps can use with the chemical bath form.
In addition, find that also the compound of formula of the present invention (I) also has the high insect effect of killing of the insect of destroying Industrial materials extremely.
Can mention following insect as preferred example, but not limited:
Beetle, for example
House longhorn beetle (Hylotrupes bajulus), Chlorophorus pilosis, furniture death watch beetle (Anobium punctatum), Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, European bamboo powder moth (Lyctus brunneus), Lyctus africanus, flat neck powder moth (Lyctus planicollis), Lyctus linearis, Lyctuspubescens, Trogoxylon aequale, Minthes rugicollis, bark beetle kind (Xyleborus spec.), Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus branneus, Simoxylonspec., and dinoderus minutus (Dinoderus minutus).
Hymenoptera (Hymenopterans), for example
The blue or green little wood wasp (Sirex juvencus) of steel, the big wood wasp of fir (Urocerus gigas), Urocerus gigas taignus and Urocerus augur.
Termite, for example
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Australia termite (Mastotermes darwiniensis), Zootermopsis nevadensis and coptotermes formosanus of taiwan (Coptotermes formosanus).
Bristle-tail, for example silverfiss (Lepisma saccharina).
Related Industrial materials are interpreted as non-living material among the present invention, for example, and preferred synthetic materials, tackiness agent, sizing material, paper and cardboard, leather, timber and wood working product and coating.
Will very particularly preferably protect and make the material that is not subjected to infestation by insect is timber and wood working product.
Can or contain a kind of like this timber of mixture protection of reagent and the wood working product is interpreted as and is with reagent of the present invention, construction timber processed goods for example, wooden frame; sleeper, bridge construction timber, harbour; wooden launch vehicle, chest, pallet; container, electric pole, wooden barrel; timber window, timber, glued board; particle board, joiner is perhaps in the Wood products of building construction or the very common use of joinery.
Active compound of the present invention can use with itself, uses with missible oil form or general conventional formulation, for example powder agent, granule, solution, suspensoid, emulsion or paste.
The preparation of mentioning can be with known method preparation itself, for example by mixed active compound and at least a solvent or thinner, emulsifying agent, dispersion agent and/or tackiness agent or fixing agent, the water repellent, randomly, siccative and UV stablizer and, if suitable, tinting material and pigment and also have other processing aid.
Be used to protect the insecticidal mixtures of timber and woodwork or the active compound of the present invention, particularly 0.001-60% weight ratio that enriched material contains 0.0001-95% weight ratio concentration.
The composition that uses or the amount of enriched material depend on species and the generation of insect, and depend on matrix.Can determine by series of trials under every kind of situation of the optimum proportion of using.But, generally speaking, using 0.0001-20% weight based on the material that will protect, the active compound of preferred 0.001-10% weight is enough.
Solvent that uses and/or thinner be organic chemistry solvent or solvent mixture and/or oil or as the organic chemistry solvent of oil or low voc solvent mixture and/or polar organic learn solvent or solvent mixture and/or water with, if suitable, emulsifying agent and/or wetting agent.
The preferred organic chemistry solvent that uses is to have greater than 35 volatilization number and be higher than 30 ℃, preferably be higher than 45 ℃ flash-point oil or as the solvent of oil.As have low volatility and in water undissolved this class oil and the material that uses as oily solvent be corresponding mineral oil or its aromatic hydrocarbon fraction, perhaps contain the preferred petroleum solvent of mineral oil, the solvent mixture of oil and/or alkylbenzene.
Advantageously using boiling spread is 170-220 ℃ mineral oil, and boiling spread is 170-220 ℃ a petroleum solvent, and boiling spread is 250-350 ℃ a spindle oil, and boiling spread is 160-280 ℃ oil or an aromatic hydrocarbon, the terebene wet goods.
In preferred embodiments, using boiling spread is 180-210 ℃ liquid aliphatic hydrocarbon or the boiling spread aromatic hydrocarbon that is 180-220 ℃ and high boiling mixture and/or the spindle oil and/or the naphthalene monochloride of aliphatic hydrocarbon, preferred α-naphthalene monochloride.
Have greater than 35 volatilization number and be higher than 30 ℃, preferably be higher than the low volatility organic oil of 45 ℃ of flash-points or can partly replace to high volatile volatile or medium volatile organic chemistry solvent as oily solvent, prerequisite is that this solvent mixture also has greater than 35 volatilization number and is higher than 30 ℃, preferably be higher than 45 ℃ flash-point, and the insecticide/fungicides mixture is soluble or emulsible in this solvent mixture.
According to embodiment preferred, part organic chemistry solvent or solvent mixture replace to the aliphatics polar organic and learn solvent or solvent mixture.The preferred aliphatics organic chemistry solvent that uses with hydroxyl and/or ester group and/or ether, glycol ether for example, ester etc.
The organic chemistry tackiness agent that uses is that synthetic resins and/or bonding dry oil itself are known, described synthetic resins and/or bonding dry oil be water-dilutable and/or in the organic chemistry solvent that uses, be soluble, dispersible or emulsible, particularly following material is formed or contained to tackiness agent by following material: acrylic resin, ethenoid resin, polyvinyl acetate for example, vibrin, polycondensation or polyaddition resin, poly-urethane resin, the Synolac of Synolac or modification, phenolic resin, hydrocarbon resin, for example indenes/coumarone resin, silicone resin, dried plant oil and/or dry oil and/or based on the physical dryness tackiness agent of natural and/or synthetic resins.
Can be as the synthetic resins that tackiness agent uses with emulsion, the form of dispersion liquid or solution is used.The pitch of maximum 10% weight or bituminous substances also can be used as tackiness agent and use.In addition, can the known tinting material of use itself, pigment, water repellent, smell are sheltered material and inhibitor or anticorrosive agent etc.
According to the present invention, composition or enriched material preferably contain the Synolac of at least a Synolac or modification, and/or a kind of dried plant oil is as the organic chemistry tackiness agent.According to the present invention, preferably use oil-contg greater than 45% weight, the Synolac of preferred 50-68% weight.
The all or part tackiness agent of tackiness agent above-mentioned can replace to fixing agent (mixture) or softening agent (mixture).These additives are for the volatilization that prevents active compound and crystallization or precipitation.The tackiness agent of the preferred 0.01-30% of replacement (based on 100% tackiness agent that uses).
Softening agent is from phthalate, dibutyl phthalate for example, dioctyl phthalate (DOP) or benzyl phthalate butyl ester, phosphoric acid ester, tributyl phosphate for example, adipic acid ester, for example hexanodioic acid two-(2-ethylhexyl) ester, stearate, for example butyl stearate or amyl stearate, oleic acid ester, for example butyl oleate, the glycol ether of glyceryl ether or higher molecular weight, glyceryl ester and p-toluenesulfonic esters.
The chemical fundamentals of fixing agent is the polyvinyl alkyl oxide, for example, and polyvinyl methyl ether, or ketone, for example benzophenone or ethylene benzophenone (ethylenebenzophenone).
Possible solvent or thinner be water particularly, if suitable, with one or more above-mentioned organic chemistry solvent or thinner, the mixing of emulsifying agent and dispersion agent.
Especially effectively the wood protection effect is to realize by a large amount of industrialization immersion methods, vacuum for example, double vacuum or pressure method.
If suitable, the instant composition can contain in addition other insecticide and, if suitable, another or several mycocide.
Insecticide and mycocide that can blended suitable counterpart is preferably mentioned among the WO94/29268.The compound of mentioning in the document is introduced the application as a reference clearly.
Mixes conjugate very particularly preferably can be an insecticide, for example poisons barnyard grass with poison, Volaton, silafluofin, nail body Cypermethrin, cyfloxylate, Cypermethrin, Deltamethrin, permethrin, Provado, NI-25, flufenoxuron, fluorine bell urea and desinsection are grand, and mycocide, for example epoxyconazole, own azoles alcohol, penta ring azoles encircles third azoles, tebuconazole, cyproconazole, metconazole, press down mould azoles, dichlofluanid, Tolylfluanid, carboxylamine 3-iodo-2-propynyl butyl ester, N-octyl group-isothiazoline-3-ketone and 4,5-two chloro-N-octyl group isothiazoline-3-ketone.
The preparation of active compound of the present invention and application can illustrate from the following examples.
The capitalization meaning of some embodiment sequence number back is the easier differences of these structures that make in the structural formula.They refer to the Q of different meanings.EXAMPLE Example I-1-a-1
Figure A9880955700951
At 60 ℃, add the compound of the 7.2g example II C-1 in the 10ml dry DMF (dimethyl formamide) in the 7.8g potassium tert.-butoxide in the 20ml dry DMF.Under this temperature, continue to stir up to react completely (by thin-layer chromatography (TCL) monitoring, mobile phase dichloromethane: ethyl acetate 5: 3), mixture under reduced pressure concentrates, resistates be dissolved in 100ml water and about 0 ℃ down with 20% intensity hcl acidifying.To precipitate suction strainer and dry.
Productive rate 4.0g (theoretical amount 61%), mp.250 ℃.Example I-1-a-2
80 ℃ with 50ml DMF in 12g potassium tert.-butoxide and 5.3g Compound I I-E stirred 2 hours.Mixture mixes with toluene and reduces pressure concentrated down.Resistates be dissolved in the 30ml frozen water and about 0 ℃ down and 20% intensity mixed in hydrochloric acid up to pH between about 5 and 6.With the mixture suction strainer and by column chromatography purifying (silica gel, dichloromethane/ethyl acetate 5/3).
Productive rate 1.15g (theoretical amount 36%), mp.163 ℃.Example I-1-a-3
Similarly, the compound from example II-B-2 obtains above-claimed cpd, mp.＞250 ℃.Example I-1-a-4
The compound for preparing the formula (I-1-a) that following table 25 lists by aforesaid method similarly.
Table 25 Example I-1-b-1
Figure A9880955700972
The compound of 2g example I-1-a-1 heated 4 hours in the 50ml ethyl acetate with 1.1ml triethylamine and 0.75g isobutyryl chloride under refluxing.Enriched mixture and resistates carry out chromatogram through silica gel, and (moving phase is hexane: acetone 7: 3).
Productive rate 1.15g (theoretical amount 48%), mp.247 ℃.Example I-1-b-2
Method by example I-1-b-1 obtains following compound, mp.189 ℃.
Figure A9880955700981
Example I-1-c-1
Figure A9880955700982
Under 0 ℃, the 0.4ml Vinyl chloroformate in the compound of the 1.3g embodiment (I-1-a-1) in the 50ml anhydrous methylene chloride and the 0.6ml triethylamine in the Dropwise 5 ml anhydrous methylene chloride, mixture stirred under not cooling off one day again.Mixture is then at every turn with 50ml 0.5N sodium hydroxide washing twice, and is dry and concentrated.Productive rate 0.70g (theoretical amount 45%), mp.196 ℃.Example I-2-a-1
Figure A9880955700991
Drip the solution of the compound of 34.6g EXAMPLE III-A-1 in the 11.22g potassium tert.-butoxide in the 100ml dry DMF, mixture at room temperature stirred.During aftertreatment, reaction mixture is joined in the hydrochloric acid of 1 liter of 1N, use dichloromethane extraction, dry and concentrated.Resistates uses ethyl acetate to carry out chromatogram through silica gel.
Productive rate 5.5g (theoretical amount 18%), mp.190-195 ℃.Example I-2-a-2
Figure A9880955700992
Under 0-10 ℃, drip the compound of the 15g EXAMPLE III-2 that is dissolved in 15mlDMF in the 6.72g potassium tert.-butoxide in 5ml DMF.Mixture at room temperature stirs and spends the night and concentrate, and resistates is dissolved in water and is using hcl acidifying with in ice-cooled.The suction strainer precipitation is also dry.
Productive rate 10.9g (theoretical amount 62%), mp.74-80 ℃.
By the method for example I-2-a-1 and I-2-a-2 and/or according to general preparation procedure, obtain the compound of following formula I-2-a: table 26
Figure A9880955701001
Example I-2-a-11
Under the room temperature, drip the compound of 9.3g embodiment (III-C-1) in the 6.5g potassium tert.-butoxide in 40ml DMF (dimethyl formamide), warm reaction mixture.Continue to stir under the room temperature after 1 day, reaction mixture is mixed with water and use dichloromethane extraction, drying is also concentrated.Water is with HCl acidifying (pH2-3) and use dichloromethane extraction.Concentrate organic phase.
Productive rate 3.40g (theoretical amount 68%), mp.272 ℃.
The compound for preparing the formula (I-2-a) that following table 27 lists by aforesaid method similarly.Table 27
Figure A9880955701012
Figure A9880955701021
Example I-2-b-1
Figure A9880955701022
Under 0-10 ℃, drip the 1.24g pivalyl chloride that is dissolved in the 10ml methylene dichloride in the compound of the 3.00g example I-2-a-1 in the 40ml methylene dichloride and the 1.52ml triethylamine.Mixture at room temperature stirs and spends the night.Reaction mixture is used 10% intensity citric acid solution successively, and sodium hydrogen carbonate solution and sodium chloride solution washing are dry and concentrated.Resistates is used hexanaphthene through silica gel chromatography: ethyl acetate 3: 1 is as moving phase.
Productive rate 1.79g (theoretical amount 47%), mp.133-136 ℃.Example I-2-b-2
Figure A9880955701031
Under the room temperature, the compound of 0.96g example I-2-b-1,0.25g O-methyl hydroxy amine hydrochloric acid salt and 1g molecular sieve 3 stirred 12 hours in 15ml methyl alcohol.Filter molecular sieve, concentrated filtrate, resistates distributes between water and methylene dichloride, dry organic phase and concentrating under reduced pressure.Resistates uses hexanaphthene: ethyl acetate 5: 1 through silica gel chromatography.
Productive rate 0.39g (theoretical amount 39%), mp.115-127 ℃.
Method by being similar to example I-2-b-1 and I-2-b-2 and/or according to general preparation procedure obtains the compound of following formula I-2-b: table 28 Example I-2-c-1
Figure A9880955701051
By being similar to the method for example I-2-b-1,, then obtain productive rate and be 46% above-claimed cpd of theoretical amount if use isopropyl chlorocarbonate to replace pivalyl chloride.mp.140-141℃。Example I-2-c-2
Figure A9880955701052
By being similar to the method for example I-2-b-1, if use the chloroformic acid iprotiazem to replace pivalyl chloride for ester, then obtaining productive rate is the oily above-claimed cpd of 1.3g.
Method by being similar to example I-2-c-1 and I-2-c-2 and/or according to general preparation procedure obtains the compound of following formula I-2-c: table 29
Figure A9880955701061
Example II-B-1
Under internal temperature 30-40 ℃, the suspension of the compound of Dropwise 5 0g embodiment XX-C-1 in the 75g vitriol oil, this mixture stirred again under this temperature 2 hours.Drip the feasible internal temperature that produces 40 ℃ of 110ml methyl alcohol in so a kind of mode then.Then continue again to stir 6 hours at 40-70 ℃.Mixture is poured in the 600g ice, mixes with sodium bicarbonate aqueous solution and uses dichloromethane extraction.
Productive rate 40g (theoretical amount 74%), mp.136-137 ℃.Example II-B-2
Figure A9880955701072
By the method for example II-B-1, obtain the above-claimed cpd of 11.7g (theoretical amount 15%) from the compound of 69g embodiment XX-B-1.mp.118-120℃。Example II-C-1
Under the room temperature, the compound of the 20g example II-B-1 in the 50ml pyridine is mixed with 4.2g O-methyl hydroxy amine hydrochloric acid salt, mixture stirred 4 hours at 50 ℃.With the mixture concentrating under reduced pressure, and resistates mixes with about 50ml water, and with dichloromethane extraction three times, the dry organic phase that merges is also concentrated.Resistates uses methylene dichloride: ethyl acetate 5: 3 through silica gel chromatography.
Productive rate 19.9g (theoretical amount 99%), mp.158-160 ℃.Example II-E-1
Under-10 to 0 ℃, with compound and the 57ml triethylamine and the 34g 2 of the 32g formula (XV) in the 200ml tetrahydrofuran (THF), 4-dimethyl benzene Acetyl Chloride 98Min. mixes, and mixture at room temperature stirred 1 day.With mixture suction strainer and concentrated.Resistates is through silica gel chromatography.
Productive rate 5.3g. 1H NMR (400MHz, d 6-DMSO): δ=2.19-2.25 (4s, 12H, ArCH 3), 4.63-4.69, and 4.82-4.86 (m, 1H, CO-O-CH), 6.9-7.06 (m, 6H, Ar-H) EXAMPLE III-1
Figure A9880955701092
Add 29.55g 2,4 in 27.90g 1-hydroxyl in 150ml toluene-4-oxo-hexahydrobenzoic acid ethyl ester, 6-trimethylphenyl Acetyl Chloride 98Min., mixture is heated overnight under refluxing.Concentrating under reduced pressure mixture then, crude product need not promptly can be used for ring-closing condensation reaction by any purifying.
Productive rate 42.9g (theoretical amount 82%), oily matter.EXAMPLE III-2
Figure A9880955701093
Under 0-10 ℃, drip 9.14g 2,4,6-trimethylphenyl Acetyl Chloride 98Min. in the compound of the 10g embodiment XXI-3 in the 100ml methylene dichloride and the 5.6g triethylamine.Mixture at room temperature stirs and spends the night.Reaction mixture washes with water, and organic phase is dry and concentrated.
Productive rate 15.14g, oily matter.
Method by being similar to EXAMPLE III-1 and III-2 and/or according to general preparation procedure obtains the compound of following formula III: table 30
Figure A9880955701111
EXAMPLE III-C-1
Figure A9880955701121
Under the room temperature, with compound and the 40g2 of the 11g embodiment (XXI-2) in the 200ml toluene, 4-dichlorophenyl Acetyl Chloride 98Min. (3.5 equivalent) mixes, mixture heated 1 day under refluxing, enriched mixture, and resistates is through silica gel chromatography, use hexane: ethyl acetate 2: 1 is as moving phase, mp.57 ℃.Embodiment XIX-1
Under the room temperature, to the ammonia solution of 414.2g 25% intensity, 139.6g ammonium chloride drips 248.3g 4-hydroxy-cyclohexanone in the mixture of 127.9g sodium cyanide and 392ml water, and mixture stirs down at 45 ℃ and spends the night, and will precipitate suction strainer and dry.
Productive rate 197g (theoretical amount 64%), mp.130 ℃.Embodiment XIX-2
Figure A9880955701123
Under the room temperature, the ammonia solution of 48.5g 25% intensity in 46ml water, 16.4g drip the compound of 36.0g embodiment XXV-1 in the mixture of ammonium chloride and 15.0g sodium cyanide, mixture stirs down at 38 ℃ and spends the night, with dichloromethane extraction and conventional processing, obtain 33.8g (theoretical amount 79%) above-claimed cpd, be oily matter.Embodiment XX-A-1
Under-20 ℃, the 79g 2,4 dichloro benzene base Acetyl Chloride 98Min. in the 1-cyano group-4-hydroxy-cyclohexyl amine of the 49g embodiment XIX-1 in 500ml THF and the 49ml triethylamine among the Dropwise 5 0ml THF.Mixture at room temperature stirred 1 day, and with 1 liter of 0.5N hcl as extraction agent, and organic phase is dry and concentrate.
Productive rate 70g (theoretical amount 61%), mp.148-150 ℃.Embodiment XX-B-1
The compound of method oxidation 70g embodiment XX-A-1 by being similar to embodiment XXV-1.
Productive rate 69.0g (theoretical amount 99%), mp.76-78 ℃.Embodiment XX-C-1
Figure A9880955701141
Under about 0 ℃, add the 40g 2,4 among the 50ml THF (tetrahydrofuran (THF)) in the compound of the 33g embodiment XIX-1 in 100ml THF and the 32ml triethylamine, 6-trimethylphenyl Acetyl Chloride 98Min., mixture at room temperature stirred 2 hours.During aftertreatment, reaction mixture and 1 liter of 1N sodium hydroxide vibration separate organic phase, and be dry and concentrated.
Productive rate 52g (theoretical amount 79%), mp.224 ℃.Embodiment XXI-1
Figure A9880955701142
Under the room temperature, the 102.0g cyclohexanedione-1 in 102ml ethanol drips the 28.7ml prussic acid in 4-monoethylene glycol (being purchased) and the 0.6ml triethylamine, and mixture at room temperature stirred 1 hour.Mixture mixes with 229ml ethanol, 0-5 ℃ down with hydrogen chloride gas saturated and stirring at room temperature spend the night.Concentrating under reduced pressure mixture and resistates at room temperature stir in 980ml water and spend the night then.The mixture dichloromethane extraction, organic phase is with saturated solution of potassium carbonate washing, and is dry and concentrated.
Productive rate 68.3g (theoretical amount 50%), oily matter.Embodiment XXI-2
Figure A9880955701151
Under-20 to 0 ℃, with the compound of the about 1 kilogram of embodiment XXX-1 in the saturated 5 liters of propyl carbinols of hydrogen chloride gas.Mixture does not spend the night under not cooling off after stirring about 3 hours under 0 ℃.
Under the vacuum, resistates mixes with about 5 premium on currency and at room temperature stirred 1 hour.Mixture is with 2.5 liters of dichloromethane extractions, and is dry and concentrated.
Productive rate 1376g (theoretical amount 81%), yellow oil.Embodiment XXI-3
Figure A9880955701152
Compound and the stirring under 50 ℃ of 0.88g O-methyl hydroxy amine hydrochloric acid salt of 1.86g embodiment XXI-1 in the 20ml pyridine are spent the night.Mixture under reduced pressure concentrates, and resistates is dissolved in water and methylene dichloride, and washs with 10% intensity citric acid, and organic phase is dried and concentrates.
Productive rate 1.7g, oily matter.Embodiment XXV-1
Figure A9880955701153
Under-70 ℃, at first in the 300ml methylene dichloride, add the 11ml oxalyl chloride.Add 10ml DMSO (methyl-sulphoxide) then, mixture stirred 3 minutes at-35 ℃.Mixture is cooled to-70 ℃ once more, and the compound that added as the 150g embodiment XXVI-1 of 10% intensity dichloromethane solution through 1 hour.Continue to stir other 15 minutes at-35 ℃, add the 130ml triethylamine, mixture at room temperature stirred 1 hour then.Mixture mixes with water carefully, with dichloromethane extraction and through filtered through silica gel.
Productive rate 7.9g (theoretical amount 56%), oily matter.Embodiment XXVI-1
Under the room temperature, the 5.7g 4-hydroxy-cyclohexanone in the 50ml pyridine mixes with 4.2g O-methyl hydroxy amine hydrochloric acid salt, and mixture stirred 4 hours at 50 ℃.Mixture concentrating under reduced pressure, resistates are dissolved in about 50ml water and with dichloromethane extraction three times.The organic phase that merges is dried and concentrates.
Productive rate 6.9g (theoretical amount 96%), oily matter.Embodiment XXVII-1
Figure A9880955701162
Add the solution of the compound of the 70.5g embodiment XXV-1 in the 1600ml ethanol in 446.4g volatile salt in 1600ml water and the 98.0g sodium cyanide, mixture stirred 10 hours at 60 ℃.Mixture is cooled to 5 ℃ and suction strainer precipitation then.
Productive rate 156.7g (theoretical amount 74%), mp.＞250 ℃.Embodiment XXX-1
Figure A9880955701163
Under the room temperature, in about 45 minutes clockwise 1004.4g 4-hydroxy-cyclohexanones and 3.70ml triethylamine, drip the 249.5g prussic acid.Mixture stirred about 1 hour at 65 ℃.
The mixture o-phosphoric acid stabilize of 0.6ml 85% intensity, and pump vacuum is dry down.Crude product need not anyly be further purified the compound of the formula of being converted into (XXI).Application Example embodiment A knurl volume aphid (Myzus) test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight, water is diluted to missible oil the concentration of expectation.
By handling the cabbage leaves (Brassica oleracea) that is seriously infected by black peach aphid (Myzus persicae) in the preparation that is immersed in the active compound of expecting concentration.
Behind the certain hour, measure and kill and wound percentage.The all aphids of 100% expression all are killed; An aphid is not killed in 0% expression.
In this test, for example prepare example I-2-b-2, I-2-c-2, I-2-b-3, I-2-b-4, I-2-a-8, I-2-a-9, I-2-b-8, I-2-c-5, I-2-b-9, I-2-c-6, I-2-b-10, I-2-b-11, I-2-b-12, I-2-c-7, after 6 days, killing-efficiency reaches 100% to the compound of I-1-a-1 and I-1-b-1 under the various situations under with illustrative 0.1% activity compound concentration.Embodiment B leafhopper (Nephotettix) test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight, water is diluted to missible oil the concentration of expectation.
By handling rice seedling (Oryzasativa) in the preparation of active compound that is immersed in expectation concentration, and the larva of standby rice green leafhopper (Nephotettixcincticeps) is infected when seedling is also moistening.
Behind the certain hour, measure the infringement percentage.The all leafhopper of 100% expression all are killed; A leafhopper is not killed in 0% expression.
In this test, for example prepare example I-2-a-2, I-2-b-3, I-2-b-4, I-2-b-5, I-2-c-2, I-2-a-5, I-2-a-6, I-2-c-3, I-2-b-7, I-2-c-4, I-2-a-7, I-2-a-9, I-2-b-9, I-2-c-6, after 6 days, killing-efficiency reaches 100% to the compound of I-1-a-1 and I-1-b-1 under the various situations under with illustrative 0.1% activity compound concentration.Embodiment C red spider (Panonychus) test solvent: 3 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound,, missible oil is diluted to the concentration of expectation with the water that contains emulsifying agent with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight.
The high approximately Japanese plum (Prunusdomestica) of 30cm that is seriously infected by the European red mite of all etap (Panonychus ulmi) with the preparation spraying of the active compound of expectation concentration.
Behind the certain hour, measure and kill and wound percentage.The all pawl mites of 100% expression all are killed; A pawl mite is not killed in 0% expression.
In this test, the compound that for example prepares example I-2-b-2 after 7 days, shows 100% effectiveness under with illustrative 0.02% activity compound concentration.Embodiment D ape chrysomelid (Phaedon) larva test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight, water is diluted to missible oil the concentration of expectation.
By handling cabbage leaves (Brassica oleracea) in the preparation of active compound that is immersed in expectation concentration, and standby horseradish ape chrysomelid (Phaedon cochleariae) larva is infected when leaf is also moistening.
Behind the certain hour, measure and kill and wound percentage.The all mealworms of 100% expression all are killed; A mealworm is not killed in 0% expression.
In this test, for example prepare example I-2-b-2, I-2-b-3, I-2-c-2, I-2-c-6, I-1-a-1, the compound of I-1-b-1 under with illustrative 0.1% activity compound concentration after 7 days in all cases kill rate reach 100%.Embodiment E meadow mythimna separata (Spodoptera frugiperda) test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight, water is diluted to missible oil the concentration of expectation.
By handling cabbage leaves (Brassica oleracea) in the preparation of active compound that is immersed in expectation concentration, and standby meadow mythimna separata (Spodoptera frugiperda) caterpillar is infected when leaf is also moistening.
Behind the certain hour, measure and kill and wound percentage.The all caterpillars of 100% expression all are killed; A caterpillar is not killed in 0% expression.
In this test, for example prepare example I-2-b-2, I-2-b-3, I-2-c-2, I-2-c-5.The compound of I-1-a-1 and I-1-b-1 under with illustrative 0.1% activity compound concentration after 7 days in all cases kill rate reach 100%.Embodiment F tetranychid (Tetranychus) test (OP resistance/immersion is handled) solvent: 3 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
In order to prepare the appropriate formulation of active compound, with active compound and the described amount solvent and the described amount emulsifier mix of 1 part of weight, water is diluted to missible oil the concentration of expectation.
The soybean plants (Phaseolus vulgaris) that seriously infects the cotton spider mites (Tetranychus urticae) of all etap is immersed in the preparation of the active compound of expecting concentration.
Behind the certain hour, measure active percentage.The all tetranychids of 100% expression all are killed; A tetranychid is not killed in 0% expression.
In this test, for example prepare example I-2-b-2, I-2-a-2, I-2-b-3, I-2-b-4, I-2-b-5, I-2-c-2, I-2-c-3, I-2-c-5, I-2-b-9, I-2-c-6, I-2-b-10, the compound of I-2-b-11 and I-1-b-1 under with illustrative 0.01% activity compound concentration after 7 days in all cases kill rate reach 100%.Embodiment GBoophilus microplus resistance/SP-resistance Parkhurst-Strain tests experimental animal: self inhaled full female insect solvent: methyl-sulphoxide
The 20mg active compound is dissolved in the 1ml methyl-sulphoxide, by preparing rarer concentration with identical solvent cut.
This test repeats 5 times and carries out.Ventrad is injected 1 μ l solution, transfers to animal in the ware and to be placed on weatherization indoor.Active after 7 days by the inhibition of laying eggs is measured.100% expression does not have tick to lay eggs.
In this test, the compound that for example prepares example I-1-a-1 and I-1-b-1 has 100% activity in all cases under the activity compound concentration with illustrative 20 μ g/ animals.Embodiment H fly larva test/growth restraining effect experimental animal: larva lucilia sericata cuprina (Lucilia cuprina) solvent: methyl-sulphoxide
The 20mg active compound is dissolved in the 1ml methyl-sulphoxide, by preparing rarer concentration with distilled water diluting.
To containing about 1cm 3Add about 20 lucilia sericata cuprina larvas in the test tube of the preparation of the active compound that horseflesh and 0.5ml will test.Measure the effectiveness of active compound after 24 hours and 48 hours.Test tube is transferred in the beaker of bottom covering sand.Again two days later, take out test tube, and the counting pupa.
After 1.5 times of times of the development time of untreated control thing, estimate the activity of active agent preparations by the fly of counting hatching.100% expression does not have fly to hatch; All flies normally hatch in 0% expression.
In this test, the compound that for example prepares example I-2-b-2 and I-1-a-1 has 100% activity in all cases when illustrative 1000ppm activity compound concentration.

Claims (13)

1. the compound of formula (I)
Figure A9880955700021
Wherein
X represents halogen, alkyl, alkenyl, alkynes base; alkoxyl group, alkenyl oxy, alkylthio, alkyl sulphinyl; alkyl sulphonyl, haloalkyl, halogenated alkenyl; halogenated alkoxy, halogenated alkenyl oxy, nitro; cyano group is perhaps represented its optional separately substituted phenyl, phenoxy group; thiophenyl, benzyl oxygen base or benzyl sulfenyl
Y represents hydrogen, halogen, and alkyl, alkenyl, the alkynes base, alkoxyl group, alkenyl oxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, haloalkyl, halogenated alkenyl, halogenated alkoxy, halogenated alkenyl oxy, nitro or cyano group,
Z represents halogen, alkyl, and alkenyl, the alkynes base, haloalkyl, halogenated alkenyl, alkoxyl group, alkenyl oxy, halogenated alkoxy, halogenated alkenyl oxy, nitro or cyano group,
N represents 0,1, and 2 or 3,
One of group below the Het representative:
Figure A9880955700022
Or
Figure A9880955700023
Wherein
G represents one of group below hydrogen (a) or the representative:
Figure A9880955700031
E (f) or
Figure A9880955700032
Wherein
E representation metal ion Equivalent or ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1Represent alkyl, alkenyl, alkoxyalkyl, alkylthio alkyl or multi-alkoxy alkyl, it is optional separately to be replaced by halogen, and representative is optional by halogen, that alkyl or alkoxyl group replace and can insert one or more heteroatomic cycloalkyl, perhaps represent phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryl oxygen base alkyl, it can be chosen wantonly separately and be substituted
R 2Represent alkyl, alkenyl, alkoxyalkyl or multi-alkoxy alkyl, it can be chosen wantonly by halogen separately and replace, perhaps representation ring alkyl, phenyl or benzyl, it can be chosen wantonly separately and be substituted,
R 3, R 4And R 5Represent alkyl independently of one another, alkoxyl group, alkylamino, dialkyl amido, alkylthio, alkenyl thio or cycloalkyl sulfenyl, it can be chosen wantonly by halogen separately and replace, and perhaps represents phenyl, benzyl, phenoxy group or thiophenyl, it can be chosen wantonly separately and be substituted,
R 6And R 7Represent hydrogen independently of one another, represent alkyl, cycloalkyl, alkenyl, alkoxyl group or alkoxyalkyl, it can be chosen wantonly by halogen separately and replace, representative can be chosen substituted phenyl wantonly, representative can be chosen substituted benzyl wantonly, perhaps represents the ring that randomly contains aerobic or sulphur with the N atom that they connected
The Q representative
Figure A9880955700033
Or
Figure A9880955700042
R 9Represent hydrogen, represent alkyl, cycloalkyl, phenyl, benzyl or heteroaryl, it can be chosen wantonly separately and be substituted, perhaps the representative or
R 10Represent hydrogen or alkyl,
R 11Represent alkyl or alkenyl,
R 12Represent alkyl or alkenyl,
M represents 0,1 or 2,
R 1 'Be independent of R 1Have above for R 1The definition that provides and
R 2 'Be independent of R 2Have above for R 2The definition that provides.
2. the compound of the formula of claim 1 (I), wherein
X represents halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-alkylthio, C 1-C 6-alkyl sulphinyl, C 1-C 6-alkyl sulphonyl, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro, cyano group perhaps represents it optional separately by halogen, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, the phenyl that nitro or cyano group replace, phenoxy group, thiophenyl, benzyl oxygen base or benzyl sulfenyl,
Y represents hydrogen, halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-alkylthio, C 1-C 6-alkyl sulphinyl, C 1-C 6-alkyl sulphonyl, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro or cyano group,
Z represents halogen, C 1-C 6-alkyl, C 2-C 6-alkenyl, C 2-C 6-alkynes base, C 1-C 6-haloalkyl, C 2-C 6-halogenated alkenyl, C 1-C 6-alkoxyl group, C 3-C 6-alkenyl oxy, C 1-C 6-halogenated alkoxy, C 3-C 6-halogenated alkenyl oxy, nitro or cyano group,
N represents 0,1, and 2 or 3,
One of group below the Het representative Or
Figure A9880955700052
G represents one of group below hydrogen (a) or the representative: E (f)Or
Figure A9880955700054
Wherein
E representation metal ion Equivalent or ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1Represent C 1-C 20-alkyl, C 2-C 20-alkenyl, C 1-C 8-alkoxy-C 1-C 8-alkyl, C 1-C 8-alkylthio-C 1-C 8-alkyl or many-C 1-C 8-alkoxy-C 1-C 8-alkyl, it can be chosen wantonly by halogen separately and replace, and representative can be chosen wantonly by halogen, C 1-C 6-alkyl or C 1-C 6That-alkoxyl group replaces and wherein one or more (particularly maximum two) not directly the methylene radical of adjacency randomly by oxygen and/or sulphur metathetical C 3-C 8-cycloalkyl,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl, C 1-C 6-halogenated alkoxy, C 1-C 6-alkyl sulfenyl or C 1-C 6The phenyl that-alkyl sulphonyl replaces,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl or C 1-C 6Phenyl-C that-halogenated alkoxy replaces 1-C 6-alkyl,
Representative is optional by halogen or C 1-C 65-that-alkyl replaces or 6-unit heteroaryl (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furyl or thienyl),
Representative is optional by halogen or C 1-C 6Phenoxy group-C that-alkyl replaces 1-C 6-alkyl, or
Representative is optional by halogen, amino or C 1-C 65-that-alkyl replaces or the heteroaryl oxygen base-C of 6-unit 1-C 6-alkyl,
R 2Represent C 1-C 20-alkyl, C 2-C 20-alkenyl, C 1-C 8-alkoxy-C 2-C 8-alkyl or many-C 1-C 8-alkoxy-C 2-C 8-alkyl, it is chosen wantonly separately and is replaced by halogen,
Representative is optional by halogen, C 1-C 6-alkyl or C 1-C 6The C that-alkoxyl group replaces 3-C 8-cycloalkyl,
Representative is optional by halogen, cyano group, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-haloalkyl or C 1-C 6Phenyl or benzyl that-halogenated alkoxy replaces,
R 3The optional C that is replaced by halogen of representative 1-C 8-alkyl is perhaps represented phenyl or benzyl, and it is optional separately by halogen, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, cyano group or nitro replace,
R 4And R 5Represent C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group, C 1-C 8-alkylamino, two (C 1-C 8-alkyl) amino, C 1-C 8-alkylthio, C 2-C 8-alkenyl thio, C 3-C 7-cycloalkyl sulfenyl, it is chosen wantonly separately and is replaced by halogen, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by halogen, cyano group, nitro, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl or C 1-C 4-haloalkyl replaces,
R 6And R 7Represent hydrogen independently of one another, represent C 1-C 8-alkyl, C 3-C 8-cycloalkyl, C 3-C 8-alkenyl, C 1-C 8-alkoxyl group or C 1-C 8-alkoxy-C 1-C 8-alkyl, it is chosen wantonly separately and is replaced by halogen, and representative is optional by halogen, C 1-C 8-haloalkyl, C 1-C 8-alkyl or C 1-C 8The phenyl that-alkoxyl group replaces, representative is optional by halogen, C 1-C 8-haloalkyl, C 1-C 8-alkyl or C 1-C 8The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one not with the methylene radical of the direct adjacency of nitrogen-atoms by oxygen or sulphur metathetical C 3-C 6-alkylidene group,
The Q representative
Figure A9880955700071
Or
Figure A9880955700073
R 9Represent hydrogen, the optional C that is replaced by halogen of representative 1-C 8-alkyl, representative is optional by halogen, C 1-C 4-alkyl or C 1-C 4The C that-alkoxyl group replaces 3-C 8-cycloalkyl is perhaps represented phenyl, benzyl or heteroaryl (for example pyridyl, pyrimidyl or thiazolyl), and it is optional separately by halogen, C 1-C 6-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group replace, and perhaps represent CO-R 1 ', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
R 10Represent hydrogen or C 1-C 8-alkyl,
R 11And R 12Be identical or different, represent C separately 1-C 6-alkyl or C 3-C 6-alkenyl,
M represents 0 or 1,
R 1 'Be independent of R 1Have above for R 1The definition that preferably provides,
R 2 'Be independent of R 2Have above for R 2The definition that preferably provides.
3. the compound of the formula of claim 1 (I), wherein
X represents fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group,
Y represents hydrogen, fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl, C 1-C 4-halogenated alkoxy, nitro or cyano group,
Z represents fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-haloalkyl, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, nitro or cyano group,
N represents 0,1 or 2,
One of group below the Het representative
Figure A9880955700081
Or
G represents one of group below hydrogen (a) or the representative:
Figure A9880955700083
E (f)Or Wherein
E representation metal ion Equivalent or ammonium ion,
L represent oxygen or sulphur and
M represents oxygen or sulphur,
R 1Represent C 1-C 16-alkyl, C 2-C 16-alkenyl, C 1-C 6-alkoxy-C 1-C 6-alkyl or C 1-C 6-alkylthio-C 1-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and perhaps representative is optional by fluorine, chlorine, C 1-C 5-alkyl or C 1-C 5The C that-alkoxyl group replaces 3-C 7-cycloalkyl,
Representative is optional by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3The phenyl that-halogenated alkoxy replaces,
Representative is optional by fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3Phenyl-C that-halogenated alkoxy replaces 1-C 4-alkyl,
Representative is optional separately by fluorine, chlorine, bromine or C 1-C 4The pyrazolyl that-alkyl replaces, thiazolyl, pyridyl, pyrimidyl, furyl or thienyl,
R 2Represent C 1-C 16-alkyl, C 2-C 16-alkenyl, C 1-C 6-alkoxy-C 2-C 6-alkyl or many-C 1-C 6-alkoxy-C 2-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine,
Representative is optional by fluorine, chlorine, C 1-C 4-alkyl or C 1-C 4The C that-alkoxyl group replaces 3-C 7-cycloalkyl,
Representative is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4-alkyl, C 1-C 3-alkoxyl group, C 1-C 3-haloalkyl or C 1-C 3Phenyl or benzyl that-halogenated alkoxy replaces,
R 3The optional C that is replaced by fluorine or chlorine of representative 1-C 6-alkyl is perhaps represented phenyl or benzyl, and it is optional separately by fluorine, chlorine, bromine, C 1-C 5-alkyl, C 1-C 5-alkoxyl group, C 1-C 3-haloalkyl, C 1-C 3-halogenated alkoxy, cyano group or nitro replace,
R 4And R 5Represent C independently of one another 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-alkylamino, two (C 1-C 6-alkyl) amino, C 1-C 6-alkylthio, C 3-C 4-alkenyl thio or C 3-C 6-cycloalkyl sulfenyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 3-alkoxyl group, C 1-C 3-halogenated alkoxy, C 1-C 3-alkylthio, C 1-C 3-halogenated alkylthio, C 1-C 3-alkyl or C 1-C 3-haloalkyl replaces,
R 6And R 7Represent hydrogen independently of one another, represent C 1-C 6-alkyl, C 3-C 6-cycloalkyl, C 3-C 6-alkenyl, C 1-C 6-alkoxyl group or C 1-C 6-alkoxy-C 1-C 6-alkyl, it is optional separately by halogen (particularly fluorine or chlorine) replacement, and representative is optional by halogen, C 1-C 5-haloalkyl, C 1-C 5-alkyl or C 1-C 5The phenyl that-alkoxyl group replaces, representative is optional by halogen, C 1-C 5-haloalkyl, C 1-C 5-alkyl or C 1-C 5The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one not with the methylene radical of the direct adjacency of nitrogen-atoms by oxygen or sulphur metathetical C 3-C 6-alkylidene group,
The Q representative
Figure A9880955700091
Or
R 9Represent hydrogen, the optional C that is replaced by fluorine or chlorine of representative 1-C 6-alkyl is represented C 3-C 7-cycloalkyl perhaps represents it optional separately by fluorine, chlorine, bromine, C 1-C 5-alkyl, C 1-C 4-alkoxyl group, C 1-C 2-haloalkyl, C 1-C 2-halogenated alkoxy, phenyl or benzyl that nitro or cyano group replace, pyrimidyl or thiazolyl are perhaps represented CO-R 1', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
Figure A9880955700101
R 10Represent hydrogen or C 1-C 6-alkyl,
R 11And R 12Be identical or different, represent C separately 1-C 4-alkyl.
M represents 1,
R 1 'Be independent of R 1Have above for R 1The definition that especially preferably provides,
R 2 'Be independent of R 2Have above for R 2The definition that especially preferably provides.
4. the compound of the formula of claim 1 (I), wherein
X represents fluorine, chlorine, and bromine, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, difluoro-methoxy, trifluoromethoxy, nitro or cyano group,
Y represents hydrogen, fluorine, and chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, difluoro-methoxy, trifluoromethoxy, nitro or cyano group,
Z represents fluorine, chlorine, and bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, difluoro-methoxy, trifluoromethoxy, nitro or cyano group,
N represents 0,1 or 2,
One of group below the Het representative
Figure A9880955700111
Or
Figure A9880955700112
G represents one of group below hydrogen (a) or the representative:
Figure A9880955700113
E (f)Or Wherein
E representation metal ion Equivalent or ammonium ion,
L represent oxygen or sulphur and
M represents oxygen or sulphur,
R 1Represent C 1-C 14-alkyl, C 2-C 14-alkenyl, C 1-C 4-alkoxy-C 1-C 6-alkyl or C 1-C 4-alkylthio-C 1-C 6-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and perhaps representative is optional by methyl, ethyl, the C that the tertiary butyl or methoxyl group replace 3-C 6-cycloalkyl,
Representative is optional by fluorine, chlorine, and bromine, cyano group, nitro, methyl, methoxyl group, the phenyl that trifluoromethyl or trifluoromethoxy replace,
Representative is optional by fluorine, chlorine, and bromine, methyl, methoxyl group, the benzyl that trifluoromethyl or trifluoromethoxy replace,
Representative is optional separately by fluorine, chlorine, and bromine or methyl substituted furyl, thienyl or pyridyl,
R 2Represent C 1-C 14-alkyl, C 2-C 14-alkenyl or C 1-C 4-alkoxy-C 2-C 6-alkyl,
The optional C that is replaced by methyl or methoxy of representative 3-C 6-cycloalkyl,
Representative is optional separately by fluorine, chlorine, and bromine, cyano group, nitro, methyl, methoxyl group, phenyl or benzyl that trifluoromethyl or trifluoromethoxy replace,
R 3The optional separately methyl that is replaced by fluorine or chlorine of representative, ethyl, n-propyl, sec.-propyl, perhaps represent phenyl or benzyl, it is optional separately by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy, trifluoromethyl, trifluoromethoxy, cyano group or nitro replace
R 4And R 5Represent C independently of one another 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino or C 1-C 4-alkylthio, it is chosen wantonly separately and is replaced by fluorine or chlorine, perhaps represents phenyl, phenoxy group or thiophenyl, it is optional separately by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 2-alkoxyl group, C 1-C 2-fluoroalkyl, C 1-C 2-alkylthio, C 1-C 2-fluoroalkane sulfenyl or C 1-C 3-alkyl replaces,
R 6And R 7Represent hydrogen independently of one another, represent C 1-C 4-alkyl, C 3-C 6-cycloalkyl, C 3-C 4-alkenyl, C 1-C 4-alkoxyl group or C 1-C 4-alkoxy-C 1-C 4-alkyl, it is chosen wantonly separately and is replaced by fluorine or chlorine, and representative is optional by fluorine, chlorine, bromine, trifluoromethyl, the phenyl that methyl or methoxy replaces, representative is chosen wantonly by fluorine, chlorine, bromine, C 1-C 4-haloalkyl, C 1-C 4-alkyl or C 1-C 4The benzyl that-alkoxyl group replaces, perhaps together representative wherein randomly one can be by oxygen or sulphur metathetical C with the methylene radical of the direct adjacency of nitrogen-atoms 5-C 6-alkylidene group,
The Q representative
Figure A9880955700121
Figure A9880955700122
Or
Figure A9880955700123
R 9Represent hydrogen, represent C 1-C 4-alkyl is represented C 3-C 6-cycloalkyl is perhaps represented phenyl or benzyl, and it is optional separately by fluorine, chlorine, and bromine, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxyl group, trifluoromethyl, trifluoromethoxy, nitro or cyano group replace, and perhaps represent CO-R 1 ', CO 2R 2 ', SO 2R 1 ', CONH 2, CONHR 11Perhaps
Figure A9880955700131
R 10Represent hydrogen or methyl,
R 11And R 12Be identical or different, represent methylidene or ethyl separately,
M represents 1,
R 1 'Be independent of R 1Have above for R 1The definition that very particularly preferably provides,
R 2 'Be independent of R 2Have above for R 2The definition that very particularly preferably provides.
5. the method for the compound of the formula (I) of preparation claim 1 is characterised in that the compound of (A) formula (II) carries out intramolecular condensation in the presence of thinner and in the presence of alkali, obtains the compound of formula (I-1-a)
Figure A9880955700132
Wherein
Q, X, Y, Z, each defines n and m in the claim 1 freely, Wherein
Q, X, Y, Z, n and m separately as above the definition and
R 8Represent alkyl,
(B) compound of formula (III) carries out intramolecular condensation in the presence of thinner and in the presence of alkali, obtains the compound of formula (I-2-a)
Figure A9880955700141
Wherein
Q, X, Y, Z, n and m be as above definition separately,
Figure A9880955700142
Wherein
Q, X, Y, Z, n, m and R 8As above definition separately,
(C) compound of formula (IV) carries out intramolecular cyclization in the presence of thinner and in the presence of acid, obtains the compound of formula (I-3-a)
Figure A9880955700143
Wherein
Q, X, Y, Z, n and m be as above definition separately,
Figure A9880955700151
Wherein
Q, X, Y, Z, n, m and R 8Separately as above the definition and
W represents hydrogen, halogen, and alkyl,
Subsequently randomly with the formula (I-1-a) that obtains, (I-2-a) and compound (I-3-a) separately
The acyl chlorides of (D α) and formula V Wherein
R 1As in the claim 1 definition and
Hal represents halogen,
Perhaps
(β) with the carboxylic acid anhydride of formula (VI)
R 1-CO-O-CO-R 1(VI) wherein
R 1As above definition;
If if suitably in the presence of thinner and suitably, in the presence of acid binding agent, react, perhaps
(E) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, react with the chloro-formic ester or the chloroformic acid thioesters of formula (VII),
R 2-M-CO-Cl (VII) wherein
R 2Each defines in the claim 1 freely with M; Or
(F) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, with the chloro monothio manthanoate or the reaction of chloro dithio formate of formula (VIII) Wherein
R 2With M as above definition separately; Perhaps
(G) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, with the SULPHURYL CHLORIDE reaction of formula (IX)
R 3-SO 2-Cl (IX) wherein
R 3As definition in the claim 1; Perhaps
(H) if if suitably in the presence of thinner and suitably in the presence of acid binding agent, with the phosphorus compound reaction of formula (X) Wherein
L, R 4And R 5Each freely in the claim 1 definition and
Hal represents halogen; Perhaps
(I) if suitably in the presence of thinner, with formula (XI) or metallic compound (XII) or amine reaction Me (OR 13) t(XI)
Figure A9880955700171
Wherein
Me represents monovalence or divalent metal,
T represent 1 or 2 and
R 13, R 14, R 15Represent hydrogen or alkyl independently of one another; Perhaps
(J α) is if if suitably in the presence of thinner and suitably in the presence of catalyzer, with the isocyanic ester or the lsothiocyanates reaction of formula (XIII)
R 6-N=C=L (XIII) wherein
R 6Each defines in the claim 1 freely with L,
Perhaps
If if (β) suitably in the presence of thinner and suitably in the presence of acid binding agent, with the urea chloride or the reaction of thiocarbamyl chlorine of formula (XIV)
Figure A9880955700172
Wherein
L, R 6And R 7Each defines in the claim 1 freely.
6. the compound of formula (II)
Figure A9880955700181
Wherein
Q, X, Y, Z, m and n separately as above the definition and
R 8Represent alkyl.
7. the compound of formula (XVII) Wherein
Q, X, Y, Z, each defines m and n in the claim 1 freely.
8. the compound of formula (III)
Figure A9880955700183
Wherein
Q, X, Y, Z, m and n separately as above the definition and
R 8Represent alkyl.
9. the compound of formula (IV) Wherein
Q, W, X, Y, Z, m and n separately as above the definition and
R 8Represent alkyl.
10. sterilant or weedicide are characterised in that, it contains a kind of compound of formula (I) of claim 1.
11. the compound pest control of the formula of claim 1 (I) and the purposes of weeds.
12. pest control and method for weed are characterised in that, make the compound of the formula (I) of claim 1 act on insect and weeds respectively, and/or its dried rhizome of rehmannia of dwelling.
13. prepare the method for sterilant or weedicide, be characterised in that the compound of the formula of claim 1 (I) mixes with expansion agent and/or tensio-active agent.
CN988095572A 1997-09-26 1998-09-12 Utilizing spirocyclic phenyl keto-enols as pesticides and herbicides Expired - Fee Related CN1217931C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19742492.9 1997-09-26
DE19742492A DE19742492A1 (en) 1997-09-26 1997-09-26 Spirocyclic phenylketoenols

Publications (2)

Publication Number Publication Date
CN1271343A true CN1271343A (en) 2000-10-25
CN1217931C CN1217931C (en) 2005-09-07

Family

ID=7843694

Family Applications (1)

Application Number Title Priority Date Filing Date
CN988095572A Expired - Fee Related CN1217931C (en) 1997-09-26 1998-09-12 Utilizing spirocyclic phenyl keto-enols as pesticides and herbicides

Country Status (14)

Country Link
US (1) US6589976B1 (en)
EP (1) EP1017674B1 (en)
JP (1) JP4422891B2 (en)
KR (1) KR100547508B1 (en)
CN (1) CN1217931C (en)
AT (1) ATE423097T1 (en)
AU (1) AU9743198A (en)
BR (1) BR9812535B1 (en)
DE (2) DE19742492A1 (en)
ES (1) ES2320394T3 (en)
TR (1) TR200000749T2 (en)
TW (1) TW568904B (en)
WO (1) WO1999016748A1 (en)
ZA (1) ZA988784B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101195599B (en) * 2003-03-14 2013-04-10 拜尔农作物科学股份公司 2,4, 6-phenyl-substituted cyclic keto-enols
CN103755716A (en) * 2005-02-22 2014-04-30 拜尔农作物科学股份公司 Spiroketal-substituted cyclic ketoenols
CN105777581A (en) * 2014-12-25 2016-07-20 沈阳中化农药化工研发有限公司 Cis-1-cyano-4-methoxycyclohexyl-2-(2, 5-dimethylphenyl)acetamide, preparation method and application thereof
WO2018171817A1 (en) * 2017-03-23 2018-09-27 浙江省化工研究院有限公司 Miticide composition containing spiro ether derivatives
CN108610315A (en) * 2016-12-09 2018-10-02 浙江省化工研究院有限公司 A kind of tetronic acid analog derivative, preparation method and application
CN112041310A (en) * 2018-04-17 2020-12-04 拜耳公司 Process for preparing N-acylated amino acid esters comprising an acid-labile ketone protecting group

Families Citing this family (91)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19818732A1 (en) * 1998-04-27 1999-10-28 Bayer Ag New aryl substituted cyclic ketoenol compounds useful for control of insects and as herbicides
DE19935963A1 (en) * 1999-07-30 2001-02-01 Bayer Ag Biphenyl substituted cyclic ketoenols
DE19946625A1 (en) 1999-09-29 2001-04-05 Bayer Ag Trifluoromethyl substituted spirocyclic ketoenols
DE10015310A1 (en) * 2000-03-28 2001-10-04 Bayer Ag Active ingredient combinations with insecticidal and acaricidal properties
DE10016544A1 (en) 2000-04-03 2001-10-11 Bayer Ag New phenyl-substituted cyclic keto-enol compounds useful e.g. as insecticides, acaricides, nematocides, acaricides, herbicides, ectoparasiticides, antifouling agents or intermediates
DE10017881A1 (en) 2000-04-11 2001-10-25 Bayer Ag Active ingredient combinations with insecticidal and acaricidal properties
DE10018370A1 (en) 2000-04-14 2001-10-18 Bayer Ag Synergistic pesticidal composition containing phenyl-substituted furanone compound and e.g. chlorfluazuron, emamectin, endosulfan, fibronil or azadirachtin, especially useful as insecticide or acaricide
AR029677A1 (en) * 2000-06-29 2003-07-10 Bayer Ag COMBINATIONS OF ACTIVE COMPOUNDS WITH INSECTICIDES AND ACARICIDES
DE10043610A1 (en) * 2000-09-05 2002-03-14 Bayer Ag Active ingredient combinations with insecticidal and acaricidal properties
DE10055941A1 (en) 2000-11-10 2002-05-23 Bayer Ag Pesticidal agent containing mixture of aryl-substituted pyrrolidine enol ethers and known insecticides or acaricides
DE10062422A1 (en) * 2000-12-14 2002-06-20 Bayer Ag Use of acetyl-CoA carboxylase to identify insecticidal use
DE10139465A1 (en) * 2001-08-10 2003-02-20 Bayer Cropscience Ag Herbicidal composition, especially for selective weed control in crops such as cereals, containing cyclic keto enol derivative herbicide and safener, e.g. cloquintocet-mexyl or mefenpyr-diethyl
DE10216737A1 (en) * 2002-04-16 2003-10-30 Bayer Ag Control of parasites in animals
DE10231333A1 (en) * 2002-07-11 2004-01-22 Bayer Cropscience Ag Cis-alkoxy-substituted 1-H-pyrrolidine-2,4-dione spirocyclic derivatives
DE10239479A1 (en) 2002-08-28 2004-03-04 Bayer Cropscience Ag New pyrrole or furan derivative spiro-cyclic ketoenol compounds, useful as pesticides, e.g. insecticides, acaricides, nematocides, ectoparasiticides, fungicides, herbicides or bactericides
DE10301804A1 (en) * 2003-01-20 2004-07-29 Bayer Cropscience Ag New 6-alkyl-2,4-dihalophenyl-substituted tetramic acid derivatives, useful as herbicides and pesticides, especially insecticides, acaricides, nematocides, ectoparasiticides and antifouling agents
DE10326386A1 (en) * 2003-06-12 2004-12-30 Bayer Cropscience Ag N-heterocyclyl-phenyl-substituted cyclic ketoenols
DE10330723A1 (en) 2003-07-08 2005-02-03 Bayer Cropscience Ag Drug combinations with insecticidal and acaricidal properties
DE10330724A1 (en) 2003-07-08 2005-01-27 Bayer Cropscience Ag Drug combinations with insecticidal and acaricidal properties
DE10353281A1 (en) 2003-11-14 2005-06-16 Bayer Cropscience Ag Combination of active ingredients with insecticidal and acaricidal properties
DE10354628A1 (en) 2003-11-22 2005-06-16 Bayer Cropscience Ag 2-ethyl-4,6-dimethylphenyl-substituted tetramic acid derivatives
DE10354629A1 (en) 2003-11-22 2005-06-30 Bayer Cropscience Ag 2-ethyl-4,6-dimethyl-phenyl substituted spirocyclic tetramic acid derivatives
KR100870174B1 (en) * 2003-12-04 2008-11-24 바이엘 크롭사이언스 아게 Active substance combination having insecticidal and acaricide properties
DE102004014620A1 (en) * 2004-03-25 2005-10-06 Bayer Cropscience Ag 2,4,6-phenyl-substituted cyclic ketoenols
DE102004030753A1 (en) 2004-06-25 2006-01-19 Bayer Cropscience Ag 3'-alkoxy spirocyclic tetramic and tri-acids
DE102004035133A1 (en) 2004-07-20 2006-02-16 Bayer Cropscience Ag Selective insecticides based on substituted cyclic ketoenols and safeners
DE102004044827A1 (en) 2004-09-16 2006-03-23 Bayer Cropscience Ag Iodine-phenyl-substituted cyclic ketoenols
DE102004053192A1 (en) 2004-11-04 2006-05-11 Bayer Cropscience Ag 2-alkoxy-6-alkyl-phenyl substituted spirocyclic tetramic acid derivatives
DE102004053191A1 (en) * 2004-11-04 2006-05-11 Bayer Cropscience Ag 2,6-diethyl-4-methyl-phenyl substituted tetramic acid derivatives
DE102005003076A1 (en) * 2005-01-22 2006-07-27 Bayer Cropscience Ag Use of tetramic acid derivatives for controlling insects of the genus of plant lice (Sternorrhyncha)
DE102005051325A1 (en) 2005-10-27 2007-05-03 Bayer Cropscience Ag Alkoxyalkyl spirocyclic tetramic and tetronic acids
DE102005059469A1 (en) * 2005-12-13 2007-06-14 Bayer Cropscience Ag Insecticidal compositions having improved activity
DE102005059891A1 (en) 2005-12-15 2007-06-28 Bayer Cropscience Ag New spiro-cyclopentyl-pyrrole or -furan derivatives, useful as pesticides, herbicides and fungicides, also new intermediates
DE102006007882A1 (en) 2006-02-21 2007-08-30 Bayer Cropscience Ag New cyclic keto enol derivatives useful for controlling animal pests and/or unwanted plant growth
DE102006014653A1 (en) * 2006-03-28 2007-10-04 Bayer Cropscience Ag Use of tetramic acid derivatives to control animal pests by drenching, drip application or soil injection
DE102006018828A1 (en) 2006-04-22 2007-10-25 Bayer Cropscience Ag Alkoxyalkyl-substituted cyclic ketoenols
DE102006022821A1 (en) 2006-05-12 2007-11-15 Bayer Cropscience Ag Use of tetramic acid derivatives for controlling insects of the order of beetles (Coleoptera), thrips (Tysanoptera), bugs (Hemiptera), flies (Diptera) and cicadas (Auchenorrhynchae)
DE102006025874A1 (en) 2006-06-02 2007-12-06 Bayer Cropscience Ag Alkoxyalkyl-substituted cyclic ketoenols
DE102006027732A1 (en) 2006-06-16 2008-01-10 Bayer Cropscience Ag Drug combinations with insecticidal and acaricidal properties
DE102006027731A1 (en) 2006-06-16 2007-12-20 Bayer Cropscience Ag Drug combinations with insecticidal and acaricidal properties
DE102006033154A1 (en) 2006-07-18 2008-01-24 Bayer Cropscience Ag Drug combinations with insecticidal and acaricidal properties
DE102006050148A1 (en) 2006-10-25 2008-04-30 Bayer Cropscience Ag New trifluoromethoxy-phenyl substituted tetramic acid-derivatives useful to combat parasites including insects, arachnid, helminth, nematode and mollusk and/or undesirable plant growth and in hygienic sectors
DE102006057036A1 (en) 2006-12-04 2008-06-05 Bayer Cropscience Ag New biphenyl substituted spirocyclic ketoenol derivatives useful for the manufacture of herbicides and for combating parasites
DE102006057037A1 (en) 2006-12-04 2008-06-05 Bayer Cropscience Ag New cis-alkoxyspirocyclic biphenyl-substituted acid derivatives used in pesticides and/or herbicides, for combating animal parasites and undesirable plant growth and as insecticides and/or acaricides in crop protection
DE102007009957A1 (en) 2006-12-27 2008-07-03 Bayer Cropscience Ag Process for improving the use of the productive potential of a transgenic plant e.g. maize, soya bean, cotton, tobacco, rice, comprises treating the plant with 3-aryl-pyrrolidin-2,4-dione compound
DE102007001866A1 (en) * 2007-01-12 2008-07-17 Bayer Cropscience Ag Spirocyclic tetronic acid derivatives
EP2014169A1 (en) 2007-07-09 2009-01-14 Bayer CropScience AG Water-soluble concentrates of 3-(2-alkoxy 4-chlorine-6-alkyl-phenyl)-substituted tetramates with their corresponding enols
EP2020413A1 (en) 2007-08-02 2009-02-04 Bayer CropScience AG Oxaspirocyclical spiro-substituted tetram and tetron acid derivatives
EP2039248A1 (en) * 2007-09-21 2009-03-25 Bayer CropScience AG Active agent combinations with insecticide and acaricide properties
EP2045240A1 (en) * 2007-09-25 2009-04-08 Bayer CropScience AG Halogen alkoxy spirocyclic tetram and tetron acid derivatives
EP2103615A1 (en) 2008-03-19 2009-09-23 Bayer CropScience AG 4'4'-Dioxaspiro-spirocyclic substituted tetramates
BRPI0822468A2 (en) * 2008-03-27 2014-10-07 Bayer Cropscience Ag USE OF TETRONIC ACID DERIVATIVES FOR THE CONTROL OF INSECTS AND SPIDER MITS BY SOIL IRRIGATION, DROPPING OR IMMERSION APPLICATION
US8404260B2 (en) 2008-04-02 2013-03-26 Bayer Cropscience Lp Synergistic pesticide compositions
EP2113172A1 (en) 2008-04-28 2009-11-04 Bayer CropScience AG Method for improved utilisation of the production potential of transgene plants
EP2127522A1 (en) 2008-05-29 2009-12-02 Bayer CropScience AG Active-agent combinations with insecticidal and acaricidal properties
TW201031327A (en) 2008-11-14 2010-09-01 Bayer Cropscience Ag Active compound combinations having insecticidal and acaricidal properties
US8389443B2 (en) 2008-12-02 2013-03-05 Bayer Cropscience Ag Geminal alkoxy/alkylspirocyclic substituted tetramate derivatives
US8846946B2 (en) 2008-12-02 2014-09-30 Bayer Cropscience Ag Germinal alkoxy/alkylspirocyclic substituted tetramate derivatives
AR075126A1 (en) 2009-01-29 2011-03-09 Bayer Cropscience Ag METHOD FOR THE BEST USE OF THE TRANSGENIC PLANTS PRODUCTION POTENTIAL
CA2754847C (en) 2009-03-11 2017-07-11 Bayer Cropscience Ag Halogenalkylmethylenoxy-phenyl-substituted ketoenols
BRPI1011208B1 (en) 2009-05-19 2018-01-02 Bayer Intellectual Property Gmbh Herbicide and pesticide compounds derived from spiroheterocyclic tetronic acid, method for the manufacture of compounds, agents for controlling pests and / or unwanted plant growth, method for controlling animal pests and / or unwanted plant growth, use of compounds, method of manufacturing agents and use of agents
DE102009028001A1 (en) 2009-07-24 2011-01-27 Bayer Cropscience Ag Use of an active agent combination (comprising a 3-phenyl-1-aza-spiro(4.5)dec-3-en-2-one compound, and an agent e.g. alanycarb, aldicarb, acephate, camphechlor or chlordane) for combating animal pests e.g. insects, acarids and helminths
WO2011098443A1 (en) 2010-02-10 2011-08-18 Bayer Cropscience Ag Spiroheterocyclical substituted tetramic acid derivatives
BR112012020084B1 (en) 2010-02-10 2017-12-19 Bayer Intellectual Property Gmbh A process for the preparation of pesticides and / or herbicides and / or fungi and / or fungi and / or fungicides and / or fungicides and / or fungicides and / or fungicides. METHOD FOR INCREASING THE ACTION OF PESTICIDES AND / OR HERBICIDES AND / OR FUNGICIDES COMPREHENDING SUCH COMPOUNDS
DE102010008643A1 (en) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 New 5'-biphenyl substituted cyclic ketoenol compounds are acetyl-coenzyme A carboxylase 1 inhibitors, useful for treating cancer e.g. breast cancer, pancreatic cancer, renal cell carcinoma, hepatocellular carcinoma and skin tumor
DE102010008642A1 (en) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 New 5'-biphenyl substituted cyclic ketoenol compounds are acetyl-coenzyme A carboxylase 1 inhibitors, useful for treating cancer e.g. breast cancer, pancreatic cancer, renal cell carcinoma, hepatocellular carcinoma and skin tumors
DE102010008644A1 (en) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 Cyclic ketoenols for therapy
WO2011131623A1 (en) 2010-04-20 2011-10-27 Bayer Cropscience Ag Insecticidal and/or herbicidal composition having improved activity on the basis of spiro-heterocyclically substituted tetramic acid derivatives
US8680316B2 (en) * 2010-12-22 2014-03-25 Bayer Cropscience Ag Process for the preparation of cis-1-ammonium-4-alkoxycyclohexanecarbonitrile salts
DK2668158T3 (en) 2011-01-25 2018-10-15 Bayer Cropscience Ag PROCEDURE FOR PREPARING 1-H-PYRROLIDINE-2,4-DION DERIVATIVES
DE102011011040A1 (en) 2011-02-08 2012-08-09 Bayer Pharma Aktiengesellschaft (5s, 8s) -3- (4'-chloro-3'-fluoro-4-methylbiphenyl-3-yl) -4-hydroxy-8-methoxy-1-azaspiro [4.5] dec-3-en-2- on (compound A) for therapy
CN103492367B (en) 2011-02-17 2015-04-01 拜耳知识产权有限责任公司 Substituted 3- (biphenyl-3-yl) -8, 8-difluoro-4-hydroxy-1-azaspiro [4.5] dec-3-en-2-ones for use in therapy
DE102011080405A1 (en) 2011-08-04 2013-02-07 Bayer Pharma AG New substituted 3-biphenyl-3-yl-8,8-difluoro-4-hydroxy-1-azaspiro(4.5)dec-3-en-2-one derivatives useful for prophylaxis or therapy of tumor diseases comprising breast cancer, prostate cancer, colorectal cancer or non-small cell lung cancer
WO2012116960A1 (en) 2011-03-01 2012-09-07 Bayer Cropscience Ag 2-acyloxy-pyrrolin-4-ones
DE102011080406A1 (en) 2011-08-04 2013-02-07 Bayer Pharma AG Substituted 3- (biphenyl-3-yl) -4-hydroxy-8-methoxy-1-azaspiro8 [4.5] dec-3-ene-2-ones
JP6212503B2 (en) 2012-01-26 2017-10-11 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Phenyl-substituted ketoenols for combating fish parasites
CN102731366A (en) * 2012-07-04 2012-10-17 浙江大学 Phenylspiro-oxime ether enol ester compound and application of phenylspiro-oxime ether enol ester compound
IL231694A (en) * 2013-03-29 2014-11-30 Sumitomo Chemical Co Process for producing nitrile compound
WO2015007640A1 (en) * 2013-07-19 2015-01-22 Syngenta Participations Ag Novel process for the preparation of spiroheterocyclic pyrrolidine diones
KR102466169B1 (en) 2016-08-04 2022-11-14 바이엘 크롭사이언스 악티엔게젤샤프트 Process for preparing spiroketal-substituted cyclic ketoenols
EP3301092A3 (en) 2018-01-26 2018-09-12 Bayer CropScience Aktiengesellschaft Process for the production of spiroketal-substituted phenylacetylamino acid esters and spiroketal-substituted cyclic ketoenols
WO2019197231A1 (en) 2018-04-10 2019-10-17 Bayer Aktiengesellschaft Method for producing spiroketal-substituted cyclic ketoenols
AU2019250600A1 (en) 2018-04-13 2020-10-22 Bayer Aktiengesellschaft Use of tetramic acid derivatives for controlling specific insects
JP7407123B2 (en) 2018-04-13 2023-12-28 バイエル・クロップサイエンス・アクチェンゲゼルシャフト Use of tetramic acid derivatives to control pests by irrigation or droplet application
WO2019197620A1 (en) 2018-04-13 2019-10-17 Bayer Cropscience Aktiengesellschaft Use of tetramic acid derivatives for controlling specific insects
WO2019197652A1 (en) 2018-04-13 2019-10-17 Bayer Aktiengesellschaft Solid formulation of insecticidal mixtures
WO2019197617A1 (en) 2018-04-13 2019-10-17 Bayer Cropscience Aktiengesellschaft Use of tetramic acid derivatives for controlling animal pests by watering, drip application plant hole treatment or furrow application
WO2020126980A1 (en) * 2018-12-18 2020-06-25 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
BR112021009703A2 (en) * 2019-03-01 2021-11-23 Bayer Ag Combinations of active compounds having insecticidal/acaricidal properties
JP2024522016A (en) 2020-09-30 2024-06-07 コントロール・ソリューションズ・インコーポレーテッド Powdered pest control composition and method of use thereof
WO2022187166A1 (en) 2021-03-01 2022-09-09 Control Solutions, Inc. Solid particulate pest control compositions and methods

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4014420A1 (en) 1989-09-23 1991-04-04 Bayer Ag 5H-FURAN-2-ON DERIVATIVES
US5207817A (en) 1989-09-23 1993-05-04 Bayer Aktiengesellschaft Herbicidal 5H-furan-2-one derivatives
DE4107394A1 (en) 1990-05-10 1991-11-14 Bayer Ag 1-H-3-ARYL-PYRROLIDIN-2,4-DION DERIVATIVES
DE4121365A1 (en) 1991-06-28 1993-01-14 Bayer Ag SUBSTITUTED 1-H-3-ARYL-PYRROLIDIN-2,4-DION DERIVATIVES
DE4216814A1 (en) 1991-07-16 1993-01-21 Bayer Ag 3-ARYL-4-HYDROXY- (DELTA) (UP ARROW) 3 (UP ARROW) -DIHYDROFURANONE- AND 3-ARYL-4-HYDROXY- (DELTA) (UP ARROW) 3 (UP ARROW) -DIHYDROTHIOPHENONE DERIVATIVES
AU666040B2 (en) * 1992-10-28 1996-01-25 Bayer Aktiengesellschaft Substituted 1-H-3-aryl-pyrrolidine-2,4-dione derivatives
DE4306259A1 (en) 1993-03-01 1994-09-08 Bayer Ag Dialkyl-1-H-3- (2,4-dimethylphenyl) pyrrolidine-2,4-diones, their preparation and their use
DE4306257A1 (en) 1993-03-01 1994-09-08 Bayer Ag Substituted 1-H-3-phenyl-5-cycloalkylpyrrolidin-2,4-diones, their preparation and their use
JP3542805B2 (en) 1993-07-02 2004-07-14 バイエル・アクチエンゲゼルシヤフト Substituted spiroheterocyclic 1H-3-arylpyrrolidine-2,4-dione derivatives, their preparation and their use as pesticides
ES2127859T3 (en) 1993-09-17 1999-05-01 Bayer Ag DERIVATIVES OF 3-ARIL-4-HIDROXI-3-DIHIDROFURANONA.
DE4337853A1 (en) * 1993-09-17 1995-03-23 Bayer Ag 3-aryl-4-hydroxy-DELTA.3 · dihydrofuranone derivatives
DE4425617A1 (en) 1994-01-28 1995-08-03 Bayer Ag 1-H-3-aryl-pyrrolidine-2,4-dione derivatives
DE4431730A1 (en) * 1994-02-09 1995-08-10 Bayer Ag Substituted 1H-3-aryl-pyrrolidine-2,4-dione derivatives
EP0754175B1 (en) * 1994-04-05 2003-01-29 Bayer CropScience AG Alkoxy-alkyl-substituted 1-h-3-aryl-pyrrolidine-2,4-diones used as herbicides and pesticides
CN1079798C (en) 1994-12-23 2002-02-27 拜尔公司 3 -aryl -tetronic acid derivatives, the production thereof and the use thereof as anti-parasitic agents
ES2224156T3 (en) 1995-02-13 2005-03-01 Bayer Cropscience Ag 1,2-PHENYL-KETOENOLES 1,2-PHENYL- SUBSTITUTED AS HERBICIDES AND PESTICIDES.
US6316486B1 (en) * 1995-05-09 2001-11-13 Bayer Aktiengesellschaft Alkyl dihalogenated phenyl-substituted ketoenols useful as pesticides and herbicides
US6110872A (en) 1995-06-28 2000-08-29 Bayer Aktiengesellschaft 2,4,5-trisubstituted phenylketo-enols for use as pesticides and herbicides
DE19602524A1 (en) * 1995-06-28 1997-01-02 Bayer Ag 2,4,5-trisubstituted phenylketoenols
EP0835243B1 (en) 1995-06-30 2003-01-29 Bayer CropScience AG Dialkyl phenyl halide-substituted keto-enols for use as herbicides and pesticides
DE19603332A1 (en) * 1995-06-30 1997-01-02 Bayer Ag Dialkyl halophenyl substituted ketoenols
CN1215390A (en) 1996-04-02 1999-04-28 拜尔公司 Substituted phenyl keto enols as pesticides and herbicides
IL128235A (en) 1996-08-05 2004-03-28 Bayer Ag 2- and 2,5-substituted phenylketoenols, processes for their preparation and arthropodicidal and nematodicidal compositions comprising them

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101195599B (en) * 2003-03-14 2013-04-10 拜尔农作物科学股份公司 2,4, 6-phenyl-substituted cyclic keto-enols
CN103755716A (en) * 2005-02-22 2014-04-30 拜尔农作物科学股份公司 Spiroketal-substituted cyclic ketoenols
TWI475955B (en) * 2005-02-22 2015-03-11 Bayer Cropscience Ag Spiroketal-substituted cyclic ketoenols
CN101160049B (en) * 2005-02-22 2016-05-11 拜耳知识产权有限责任公司 Spiroketal-substituted cyclic ketoenols
CN105777581A (en) * 2014-12-25 2016-07-20 沈阳中化农药化工研发有限公司 Cis-1-cyano-4-methoxycyclohexyl-2-(2, 5-dimethylphenyl)acetamide, preparation method and application thereof
CN108610315A (en) * 2016-12-09 2018-10-02 浙江省化工研究院有限公司 A kind of tetronic acid analog derivative, preparation method and application
WO2018171817A1 (en) * 2017-03-23 2018-09-27 浙江省化工研究院有限公司 Miticide composition containing spiro ether derivatives
CN112041310A (en) * 2018-04-17 2020-12-04 拜耳公司 Process for preparing N-acylated amino acid esters comprising an acid-labile ketone protecting group
CN112041310B (en) * 2018-04-17 2023-11-03 拜耳公司 Method for producing N-acylated amino acid esters comprising ketone protecting groups with acid-instability

Also Published As

Publication number Publication date
TW568904B (en) 2004-01-01
JP2001518464A (en) 2001-10-16
CN1217931C (en) 2005-09-07
KR100547508B1 (en) 2006-02-01
DE19742492A1 (en) 1999-04-01
ATE423097T1 (en) 2009-03-15
WO1999016748A1 (en) 1999-04-08
ES2320394T3 (en) 2009-05-21
US6589976B1 (en) 2003-07-08
EP1017674A1 (en) 2000-07-12
BR9812535B1 (en) 2009-12-01
JP4422891B2 (en) 2010-02-24
ZA988784B (en) 1999-03-31
TR200000749T2 (en) 2000-08-21
DE59814345D1 (en) 2009-04-02
EP1017674B1 (en) 2009-02-18
AU9743198A (en) 1999-04-23
BR9812535A (en) 2000-07-25
KR20010023904A (en) 2001-03-26

Similar Documents

Publication Publication Date Title
CN1217931C (en) Utilizing spirocyclic phenyl keto-enols as pesticides and herbicides
CN1156470C (en) New Substituted pyridyl keto enols
CN1130366C (en) Substituted phenylketoenols and their use as pesticides and herbicides
CN100339352C (en) 2-and 2,5-substituted phenylketoenols
CN1280271C (en) Arylphenyl-substituted cyclic keto-enols
CN1131209C (en) Alkyl dihalogenated phenyl-substituted ketoenols useful as pesticides and herbicides
CN1152860C (en) Dialkyl phenyl halide-substituted keto-enols for use as herbicides and pesticides
CN1128802C (en) Phenyl-substituted cyclic ketoenol
CN1154634C (en) 2 -phenyl -substituted heterocyclic 1, 3 -keonols as herbicides and pesticides
CN1319929C (en) Aryl phenyl substituted cyclic ketoenols
CN1207281C (en) Trifluoromethyl-substd. spirocyclic ketoenols
CN1309709C (en) C2 phenyl-substituted cyclic keto-enols used as pesticides and herbicides
CN1247541C (en) Cyclic imines as pesticides
CN1119310C (en) Cyclopentane-1,3-dione derivatives
CN1215390A (en) Substituted phenyl keto enols as pesticides and herbicides
CN1207737A (en) Oxymethoxy-3-aryl-pyrone derivs.
CN1207093A (en) Substituted thiazolines and their use for controlling animal pests
CN1309643A (en) Diphenylimidazolines
CN1865219A (en) 2- and 2,5-substituted phenylketo-enols
CN1206413A (en) 3-aryl-5-halogen-pyrone derivative

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1032056

Country of ref document: HK

ASS Succession or assignment of patent right

Owner name: BAYER INTELLECTUAL PROPERTY GMBH

Free format text: FORMER OWNER: BAYER AKTIENGESELLSCHAFT

Effective date: 20150610

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150610

Address after: German Monheim

Patentee after: Bayer Pharma Aktiengesellschaft

Address before: Germany Leverkusen

Patentee before: Bayer Aktiengesellschaft

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20050907

Termination date: 20160912

CF01 Termination of patent right due to non-payment of annual fee